Photoillumination with 405 nm laser causes shifts in XPS peaks of n-Si(100), and CdS. To distinguish between surface photovoltage (SPV), and charging, dynamical measurements are performed, while sample is subjected to square wave pulses of ± 10.00 V amplitude, and 10-3-10 5 Hz frequency. For n-Si, Si2p peaks are twinned at + 10.00 and -10.00, yielding always 20.00 eV difference. Photoillumination shifts the twinned peaks to higher energies, but the difference is always 20.00 eV. However, for CdS, the measured binding difference of Cd3d peaks exhibits strong frequency dependence due to charging, which indicates that both fast SPV and slow charging effects are operative.