Yes, all the authorized users and groups that have been granted DB2 access are in the catalog somewhere, and you can query it with SQL. You may have to check several of the "AUTH" tables, depending on what you are looking for.
However, the DB2 catalog does not contain all the users and groups, just the ones who have already been granted DB2 access. You would have to issue an operating system command to get all the users and groups. You could write a C Stored Procedure to issue the OS commands.
When you grant access to DB2 objects in the Control Center, it gets a list of users or groups from the OS.