This may be a moot point, but to check and see if the username already exists, I would issue the following request (a small modification to the shamittomar request):
SELECT DISTINCT `username` FROM `users` WHERE `username` = 'webdev';
This, by default, returns a single instance of "webdev" in the "username" column; if you add more parameters, however, this may change your results. For example, if you run
SELECT DISTINCT `user_id`, `username` FROM `users` WHERE `username` = 'webdev';
"user_id" "username".