Photoelectron emission measurements have been performed using a room-temperature 14 GHz ECR ion source. It is shown that the photoelectron emission from Al, Cu, and stainless steel (SAE 304) surfaces, which are common plasma chamber materials, is predominantly caused by radiation emitted from plasma with energies between 8 eV and 1 keV. Characteristic X-ray emission and bremsstrahlung from plasma have a negligible contribution to the photoelectron emission. It is estimated from the measured data that the maximum conceivable photoelectron flux from plasma chamber walls is on the order of 10% of the estimated total electron losses from the plasma.