Yes, this is possible, provided that the users have the appropriate permissions to use the feature.  For example, if you have 250 concurrent user licenses, you could schedule 500 total agents: 250 agents for the morning and 220 agents for the afternoon. For more information about the necessary permissions, see Workforce management permissions overview.

If your organization has concurrent licenses, your billable user count is based on the concurrent peak for the set of users who used WEM features (for example WFM schedules) at some point in a given billing month.