Neither of those is immediate. It still takes 3 days to cash out.
But apparently you can use Western Union to send actual cold hard cash anywhere immediately. I know, I was surprised too, wouldn't know if my girlfriend didn't work there.
There are many services of this kind. Some (like Western Union, MoneyGram and Ria) have agents all over the world. Others are specific to certain corridors, often serving a specific diaspora. There's also the hawala system (http://en.wikipedia.org/wiki/Hawala).
I think they have some weird security rules. The 21 day thing happened to my brother after his first ebay sale. He phone them though and they released it immediately after verifying a few things.
Paypal? Venmo?