Formic acid (FA) is a promising in situ H 2 carrier for fuel cell applications due to its high energy density and liquid state under ambient conditions. The development of active and cost-effective catalysts for FA decomposition is essential for efficient hydrogen production. In this study, Pd/rGO and Pd–Ag/rGO catalysts were synthesized via an in situ chemical reduction method and evaluated for liquid-phase FA dehydrogenation. Pd–Ag catalysts with varying Pd : Ag ratios were prepared using different synthesis approaches to investigate the effect of alloy composition on catalytic performance. A 10 wt% Pd/rGO catalyst exhibited high hydrogen yield and was selected as the reference for alloying with Ag to reduce Pd usage and cost. By combining catalytic performance evaluation, physicochemical characterization, and density functional theory (DFT) calculations, the key factors governing FA decomposition over Pd–Ag catalysts were identified. Among the tested compositions, the Pd 40 Ag 60 /rGO catalyst achieved the highest turnover frequency (TOF) of 1323 h −1 , indicating an optimal balance between activity and Pd utilization. DFT calculations reveal that Ag weakens hydrogen adsorption on Pd active sites, providing mechanistic insight for the rational design of highly dispersed Pd-based alloy catalysts for efficient FA dehydrogenation, contributing to the advancement of formic acid as a hydrogen carrier.