Two dimensional layered transition metal dichalcogenides (TMDS) have immense potential as inexpensive electro-catalyst for hydrogen evolution reaction (HER). Modification of crystal and electronic structure is a promising strategy to enhance the catalytic performance of TMDS. Herein, a colloquial solvothermal method was used to prepare the vanadium (V) doped MoS2 (VMSd). The structural, morphological and chemical analysis confirmed the formation of highly pure and uniform VMSd nanoflower. Tuning of V content in MoS2 successively improved its catalytic activity towards hydrogen evolution reaction (HER). As, evident from the polarization curve, the VMSd required low overpotential of 194 and 206 mV to achieve benchmarking current density of 10 mA cm−2 in acidic and basic medium, respectively. Mott-Schottky analysis suggested that the flat band potential of MoS2 differed upon V-doping, resulting in alteration of charge transfer ability at the electrode-electrolyte interface. The Fermi level shifted towards the conduction band with optimized V-doping and the band structure got modified effectively
