A modification of photoreflectance spectroscopy, which improves the precision and efficiency of measuring time-evolving surface electric fields, is proposed. This modification is explored for studying the band bending evolution under cesium adsorption on the reconstructed GaAs(001) surface and relaxation processes in the non-equilibrium adsorbate overlayer. Observation of several distinct maxima and minima in the coverage dependence of the band bending can be explained by the formation of adatom-induced surface states with a quasi-discrete spectrum.