To understand the different mechanism occurring at the MoS2-silicon interface, we have fabricated a MoS2/Si heterojunction by exfoliating MoS2 on top of the silicon substrate. Raman spectroscopy and atomic force microscopy (AFM) measurement expose the signature of few-layers in the deposited MoS2 flake. Herein, the temperature dependence of the energy barrier and carrier density at the MoS2/Si heterojunction has been extensively investigated. Furthermore, to study band alignment at the MoS2/Si interface, we have calculated a valence band offset of 0.66 ± 0.17 eV and a conduction band offset of 0.42 ± 0.17 eV using X-ray and Ultraviolet photoelectron spectroscopy. We determined a type-II band alignment at the interface which is very conducive for the transport of photoexcited carriers. As a proof-of-concept application, we extend our analysis of the photovoltaic behavior of the MoS2/Si heterojunction. This work provides not only a comparative study between MoS2/p-Si and MoS2/n-Si heterojunctions but also paves the way to engineer the properties of the interface for the future integration of MoS2 with silicon. © 2018 Author(s).