We fabricated Si nanopillar (NP) arrays using e-beam lithography and coated them with poly(3-hexylthiophene-2,5-diyl) (P3HT) organic semiconductor layers. Optical reflection spectra showed that Mie resonance significantly increased the scattering cross-sections of the NPs and strongly concentrated incident light in the NPs. Such concentrated light should produce numerous charge carriers and affect the subsequent drift/diffusion of the carriers. Surface photovoltage (SPV), defined as the difference of the surface potential in dark and under light, could reveal the formation and separation of the photo-generated carriers. Especially, Kelvin probe force microscopy technique allowed us to obtain real space SPV maps with nanoscopic spatial resolution. The SPV values at the NP tops were much larger than those at the flat regions around the NPs. This study would provide us insights into improving performance of organic/inorganic hybrid nanostructure-based devices.