By incorporating laser illumination, and/or by application of electrical square-wave pulses to the sample, X-ray photoelectron spectroscopy is utilized to probe the dynamics of the surface structures in the range of 10-3 to 105 Hz. Different experimental methodologies are introduced, and their applications to investigate certain dynamical properties of two compound semiconductors, CdS and GaN are given. It is shown that dynamics of charging/discharging and surface photovoltage formation and its dissipation, and entanglement of various processes can be investigated by following the voltage shifts recorded in a chemical specific fashion.