Hydrogen (H2) generation by electrochemical water splitting is a key technique for sustainable energy applications. Two-dimensional (2D) transition-metal dichalcogenide (MoS2) and silver phosphate (Ag3PO4) possess excellent electrochemical hydrogen evolution reaction (HER) properties when they are combined together as a composite rather than individuals. Reports examining the HER activity by using Ag3PO4, especially, in combination with the 2D layered MoS2 are limited in literature. The weight fraction of MoS2 in Ag3PO4 is optimized for 1, 3, and 5 wt%. The Ag3PO4/1 wt % MoS2 combination exhibits enhanced HER activity with least overpotential of 235 mV among the other samples in the acidic medium. The synergistic effect of optimal nano-scale 2D layered MoS2 structure and Ag3PO4 is essential for creating higher electrochemical active surface area of 217 mF/cm2, and hence this leads to faster reaction kinetics in the HER. This work suggests the advantages of Ag3PO4/1 wt % MoS2 heterogeneous composite catalyst for electrochemical analysis and HER indicating lower resistivity and low Tafel slope value (179 mV/dec) among the prepared catalysts making it a promising candidate for its use in practical energy applications.