The User report type does not offer the ability to display whether or not the Service Feature (formerly Service Cloud) license field is checked on User records.
Instead, you can use Developer Console or Data Loader to export the User details and determine which users have this license assigned.
The field on the user object that holds the "Service Cloud User" checkbox value is 'UserPermissionsSupportUser'.
Export a list of users with the Service Cloud User checkbox enabled by adding a conditional filter to a Data Loader export or query against the User object:
See the Export Data documentation for more details on how to export via Data Loader.
If your organization would like to see the ability to report on Service Users added in the future, consider voting for the following idea in the Idea Exchange: Gain the ability to report on Live Agent and Service users.
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