We present a study of the effect of gold nanoparticles (Au NPs) on TiO₂ on charge generation and trapping during illumination with photons of energy larger than the substrate band gap. We used a novel characterization technique, photoassisted Kelvin probe force microscopy, to study the process at the single Au NP level. We found that the photoinduced electron transfer from TiO₂ to the Au NP increases logarithmically with light intensity due to the combined contribution of electron-hole pair generation in the space charge region in the TiO₂-air interface and in the metal-semiconductor junction. Our measurements on single particles provide direct evidence for electron trapping that hinders electron-hole recombination, a key factor in the enhancement of photo(electro)catalytic activity.