We have installed WordPress Multisite (Network) and created some sites.
On the main site admin > users, it displays some users from other sites listed as subscriber user.
Please advice how this possible?
That is expected behaviour.
From the codex on Multisite Network Administration:
By design, all users who are added to your network will have subscriber access to all sites on your network. To allocate a different default role for users on individual sites, you must use a plugin, such as Multisite User Management.