Feel free to submit a PR if anything isn't covered, or you've had a different experience than what's here.
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Don't ask for more than you need
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Do not resell samples (this is why TI stopped sending samples to students)
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Be prepared for a barrage of phone calls from some manufacturers.
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You may be questioned about the use of samples. Know your project
Some companies use samplecomponents to process samples. This is a google query that'll find all of them site:samplecomponents.com/scripts/samplecenter.dll?*?cmd=menu "sample center" Please report back anything useful
Microchip The Best. They make all kinds of stuff. I used my personal email. They do not accept common emails such as @gmail.com. I have ordered from there somewhat frequently and they do not bug you / "follow up". DHL WPX
NXP Pretty good. They even offer free "priority" shipping if you click the button that asks. FedEX Express.
Renesas Pretty good. They send samples of cheap stuff within a week and also fulfilled my requests for more expensive parts. FedEX Express.
Micron IC's / Microcontrollers. Sends samples free via USPS Priority Mail. Takes 1+ months.
TE Passives, Connectors, Switches. TE Connectivity. Pretty good. Sent multiple orders with more expensive parts. All were shipped very quickly. I got 1 email from sales, but they haven't bugged me. FedEX Express.
Amphenol ICC Connectors. Sent my connectors using UPS Saver. Pretty quick turnaround.
Nexperia ICs. Writing the sales office a short email about your project is the way to go. Very quick response and delivery.
Analog Devices I've tried with a academic email, no luck with form on website and no luck using their sample center either.
Maxim Integrated Sends samples only if you have a corporate/school email. Quick turnaround (3 days) and uses DHL Express WPX. Now part of Analog Devices. Used to be great!
Texas Instruments (National Semi) TI says that samples requests are only for professional engineers and fobs you off to the TI Store.
Microchip The Best. They make all kinds of stuff. I used my personal email. They do not accept common emails such as @gmail.com. I have ordered from there somewhat frequently and they do not bug you / "follow up". DHL WPX
Silicon Laboratories Sent request and was shipped quickly via DHL WPX
STMicroelectronics Ordered and sent DHL non tracked. $7 for shipping to Australia. Occasionally they have free shipping offers. Some very nice MOSFETS and other IC's.
ON Semiconductor Only paid samples from distributor. ON wants $15 for shipping + $5 for handling. Have not tried.
NXP Pretty good. They even offer free "priority" shipping if you click the button that asks. FedEX Express.
Cirrus Logic Haven't tried yet
Allegro Microsystems No option for samples on website.
Sensirion No free samples at the moment.
Central Semi Website is broken. Uses old recapcha.
Zilog Requested samples and recieved a few months later.
Austria Microsystems Gotten samples with no "follow up". DHL Express WPX.
Macronix International Will not send samples unless you are a business and have account number
Renesas Pretty good. Sent samples of cheap stuff within a week and also fulfilled my requests for more expensive parts. FedEX Express.
Micron IC's / Microcontrollers. Sends samples free via USPS Priority Mail. Takes 1+ months.
Micro Crystal Real Time clock and crystal oscilator. Sends a demo bard and 5 pieces sample. Forwarded my details to annoying distirbutor. FedEX Express.
Nexperia ICs. Writing the sales office a short email about your project is the way to go. Very quick response and delivery.
Monolithic Power Systems Power and amplifiers. Have not tried.
Vishay They don't send samples (if) you can find a part that Vishay "stocks"
TE TE Connectivity. Pretty good. Sent multiple orders with more expensive parts. All were shipped very quickly. I got 1 email from sales, but they haven't bugged me. FedEX Express
Würth Elektronik Pretty good. Sales rep called me next day to check on project and to ask how I found out about them, etc. FedEX Express.
Bivar They do not send samples and want you to buy them.
Lite-On No response yet.
TE Connectivity. Sent multiple orders with more expensive parts. I got 1 email from sales, but they haven't bugged me. FedEX Express.
SamTec No response yet.
Mill-Max Happy to send samples, UPS, got a pretty nice pocket magnifier as well.
Desco / Charleswater Will only send to "professional engineers"
ITW/Fastex Have not tried.
Keystone electronics They sent my request to a distributor who has not contacted me.
Metz Connect Have not tried.
Memory Protection Devices No form for samples on website. Have not tried emailing them.
Norcomp Need shipping account. Have not tried.
Amphenol ICC Sent my connectors using UPS Saver. Pretty quick turnaround.
3M Their website is hard to navigate and I cannot find a samples request form for Australia.
PacTec Enclosures Have not tried.
OKW Enclosures - No responce.
Serpac No responce.
Hammond Manufacturing No sampling option on webpage. Have not tried.
NKK Switches Shipping account required if you want UPS or FedEx. Have not tried.
TE Connectivity. Sent multiple orders with more expensive parts. I got 1 email from sales, but they haven't bugged me.
MicroMetals No option on website. Have not tried.
Fox Electronics No responce.
Purdy Electronics No form on website. They will send you off to a distributor to buy it.
RichCo Inc Have not tried.
Coilcraft Inductors, Transformers and other high-quality magnetics. They are very generous with samples. You can contact a sales rep, and they will provide you with samples regardless of if you are working, a student or just an independent hobbyist. Contacting them through a regular E-Mail domain (e.g. @gmail.com) also works.
Parallax No form on website. They said they do not do samples.
LittelFuse Have not tried.
Bourns No samples. Hello James, Thank you for your interest in Bourns’ products. Please visit our website (www.bourns.com) for a list of authorised online channel partners to purchase the required parts.
Ametherm Free shipping only for usa and Canada. Have not tried.
AVX Corporation No responce.
KOA Speer Electronics Sales rep emailed me saying they do not send samples.
Central Technologies Have not tried.
API Delevan Have not tried.
SJS Products Have not tried.
Ecliptek No response.
Taoglas Shipping account required.
Eaton No responce.