You should not use thermostatic radiator valves (TRVs) in the same room as the wall-mounted thermostat.
If both thermostats are in the same area they will compete to increase and decrease the radiators heat. This means that the room might not reach the ambient temperature that you want.
Some boilers require one radiator without a TRV to keep the system working correctly. Having at least one non-TRV will ensure a minimum flow of water through the boiler and prevent any damage.
It is also best to avoid using TRVs in the bathroom as the heat in that space can cause the capsule to expand and shut the TRV down.