Seems like a service like this could swing both ways. I love how everyone assumes paying someone to solve captcha's would be used for spam purposes, but I can think of a pretty big legitimate reason: time. Creating accounts and then entering captcha's can be very time consuming.
If you can pay someone a few dollars to solve captcha's for legitimate use, entering the captcha for you and whatnot, you've saved a whole heap of time you could be using on other things like your startup.
I think the underlying service is really for people to create spam accounts on Facebook and Gmail (as Rob mentioned), but I could see legitimate uses for it (as I mentioned above) as well.