When trying to add a serial key to Devolutions Hub Business, if there are already a greater number of users created for that Devolutions Hub than the maximum number of users for that key, it will give the "Invalid Devolutions Hub Business serial key" error.
Solution
Contact the Devolutions sales department to adjust the number of users needed for that license.
Alternatively, if some users were created by mistake, the administrator can delete them by going through the web interface to Administration – Users.