The effect of localized electron states on the photovoltage at a free semiconductor surface is analyzed. The analysis shows that surface-photovoltage spectroscopy (SPS) is inherently more sensitive to surface states than to bulk states. Moreover, a fundamental difference between the effect of surface and bulk states on the surface photovoltage (SPV) is shown. The analysis demonstrates that the same illumination-induced variation of the population at a surface and a bulk state may result in a significantly different dependence of the SPV on the illumination intensity. Under certain conditions, this difference makes it possible to distinguish between surface and bulk states by means of SPS. Analytical expressions for these relations are obtained under the depletion approximation, and are compared with the results of a numerical simulation. Experimental results obtained from InP samples demonstrate an application of the theory to practical distinction between surface and bulk states.