Abstract Large signal photovoltage pulses, measured on real surfaces of high-resistivity p-type silicon as a function of excitation intensity and induced charge, show characteristic features, especially smooth minima in the negative pulses. It is shown how the results can be used for a determination of surface potentials (band bendings) and surface- or interface-state distributions. Comparisons between theoretically and experimentally determined photovoltages show that the exchange of charge carriers between surface states and space charge layer during electron-hole nonequilibrium was not negligible and has to be taken into account for an accurate determination of surface potentials. The influence of such trapping processes is analysed graphically and analytically for continuously distributed surface states and the modifications due to trapping are determined. It is shown that the bands become asymptotically flat for the limit of large excitation even when strong trapping in a system of continuously distributed surface states with arbitrarily large concentrations prevails.