The logo looks like the letters C and a. I wonder whether this is intentional.
Probably a nod to the @username format that Twitter made so popular.
I remember hashtags being popularized first by Flickr (maybe @mentions were too?)
IRC, chat rooms, web forums. Pretty much any sort of group social arena.
The symbol lends itself to the usage, not vice versa. That's like asking "why do people use quotation marks around quotes"; because that's its intention.