We report characterization of photovoltaic and photoconductivity effects on nanostructured surfaces through light induced changes in the X-ray photoelectron spectra (XPS). The technique combines the chemical specificity of XPS and the power of surface photovoltage spectroscopy (SPV), with the addition of the ability to characterize photoconductivity under both static and dynamic optical excitation. A theoretical model that quantitatively describes the features of the observed spectra is presented. We demonstrate the applicability of the model on a multitude of sample systems, including homo- and heterojunction solar cells, CdS nanoparticles on metallic or semiconducting substrates, and carbon nanotube films on silicon substrates.