In these types of systems, you don't usually assign any user data (i.e., user names) before the invitee has actually signed up, and it may be a bit of a pain to get that kind of URL working depending on the framework you're using.
The process is normally:
- Invite a user, which sends them an e-mail.
- Invitee clicks through a link in the e-mail to go to the site's main registration page.
- Invitee registers with a valid user name of their choosing, and based on some unique random key (included in the clickthrough link), you can do your business logic with the two users involved (add to friends list, or whatever).
The drawback to generating your own user names is that they're more likely to be guessed than a random number, because you'll likely use English words in them. If you generate and assign random user names (i.e., "s243k2ldk8sdl"), the invitee is not going to be pleased since they have to do extra work to change the user name, or somehow remember that name.
EDIT, since I didn't understand the question very well.
I think the scheme is fine, except I would just use the invitor's user name in the URL and not allow them to change it (why allow it?). The only issue is if there is some kind of limit put on the number of invites (or maybe there is a reward for each invite), where you'd want to secure each clickthrough with some kind of unique hash value only valid for the invitor's URL.
EDIT 2
Since the users in the system do not have user names assigned, you could go either way. Allowing "user name" assignment on a first-come, first-served basis would be fine, as this would let everyone share their URL more easily with friends since it's memorable and can simply be typed in. However, that goes out the window if a unique key is required to sign up... in which case, it's going to be simpler to just not implement the user name thing and direct everyone to a single registration page of some kind.