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He doesn't have to authorize your Steam user on the device you're to play his library on. (The 5 authorized users can access his library from ANY of the 10 authorized devices above anyway.)
So you could try seeing if it's any different if you log in on your Steam -account on some other computer and then see if he can tick your Steam user from the tickbox list on that PC. (He doesn't have to authorize that other computer though.)
I'm suggesting to see if your name shows up on the list if tried on another device.
EDIT: Also, no the account does not show up on another device either.
You should then be able to access his Steam -library while on any of the authorized devices (of which your primary computer should be one of.)
EDIT
Ah, have you tried authorizing the computer you're on with the account that doesn't show up on the list?
Have you tried authorizing the computer with the account that doesn't show up?
http://store.steampowered.com/account/managedevices
Then have him re-apply it.
I was trying to share with my brother but it wasn't working. Login here, login there, login back, but nothing. I found that the DEVICE WAS NOT BEEN RECORDED as AUTHORIZED DEVICE.
(You can check that it is not on the list from your account)
Instead of uninstalling everything, there's a easy way out.
Make sure that your friend's user name is checked on Family Share as a usual, and after that try this:
1) In your device, log off from your account and login with your friend's account. At your friend account, start download any game that is not yours. You DON'T need to completely, only need to start downloading.
2) Log off and Log back to your account.
3) Your friend's game will be on your library, only that game. Select that, try to download and you'll have to borrow it from your friend. Insert a familiar name to your device and confirm.
4) Your friend will receive an e-mail asking to authorize. Confirm it.
5) After that, EVERY OTHER GAMES will be available on your library.
In the end, this is only a way to add the DEVICE to AUTHORIZED LIST. But finally it worked for us.
Do the same for your friend and he will have the access to your games.
It's old but it still works! My son is home sick from school and sharing just stopped working for no apparent reason. Your fix go it working again, so thank you so much!