We prepared MoS2 monolayers on Au nanodot (ND) and nanohole (NH) arrays. Both these sample arrays exhibited enhanced photoluminescence intensity compared with that of a bare SiO2/Si substrate. The reflectance spectra of MoS2/ND and MoS2/NH had clear features originating from excitation of localized surface plasmon and propagating surface plasmon polaritons. Notably, the surface photovoltages (SPV) of these hybrid plasmonic nanostructures had opposite polarities, indicating negative and positive charging at MoS2/ND and MoS2/NH, respectively. Surface potential maps, obtained by Kelvin probe force microscopy, suggested that the potential gradient led to a distinct spatial distribution of photo-generated charges in these two samples under illumination. Furthermore, the local density of photo-generated excitons, as predicted from optical simulations, explained the SPV spectra of MoS2/ND and MoS2/NH. We show that the geometric configuration of the plasmonic nanostructures modified the polarity of photo-generated excess charges in MoS2. These findings point to a useful means of optimizing optoelectronic characteristics and improving the performance of MoS2-based plasmonic devices. © 2020 American Chemical Society.