In this study, a systematic investigation of MoS2 nanostructure growth on a SiO2 substrate was conducted using a two-stage process. Initially, a thin layer of Mo was grown through sputtering, followed by a sulfurization process employing the CVD technique. This two-stage process enables the control of diverse nanostructure formations of both MoS2 and MoO3 on SiO2 substrates, as well as the formation of bulk-like grain structures. Subsequently, the addition of reduced graphene oxide (rGO) was examined, resulting in MoS2/rGO(n), where graphene is uniformly deposited on the surface, exposing a higher number of active sites at the edges and consequently enhancing electroactivity in the HER. The influence of the synthesis time on the treated MoS2 and also MoS2/rGO(n) samples is evident in their excellent electrocatalytic performance with a low overpotential.