Metal and transition-metal dichalcogenide (TMD) hybrid systems have been attracting growing research attention because exciton-plasmon coupling is a desirable means of tuning the physical properties of TMD materials. Competing effects of metal nanostructures, such as the local electromagnetic field enhancement and luminescence quenching, affect the photoluminescence (PL) characteristics of metal/TMD nanostructures. In this study, we prepared TMD MoS2 monolayers on hexagonal arrays of Au nanodots and investigated their physical properties by micro-PL and surface photovoltage (SPV) measurements. MoS2 monolayers on bare Au nanodots exhibited higher PL intensities than those of MoS2 monolayers on 5-nm-thick Al2O3-coated Au nanodots. The Al2O3 spacer layer blocked charge transfer at the Au/MoS2 interface but allowed the transfer of mechanical strain to the MoS2 monolayers on the nanodots. The SPV mapping results revealed not only the electron-transfer behavior at the Au/MoS2 contacts but also the lateral drift of charge carriers at the MoS2 surface under light illumination, which corresponds to nonradiative relaxation processes of the photogenerated excitons. © 2020 American Chemical Society.