A bimetallic Ni–Pd alloy nanoparticle catalyst with a low palladium content (Ni0.90Pd0.10 nanocatalyst) was prepared and its catalytic performance in Suzuki–Miyaura reactions was evaluated along with that of other Ni–Pd nanocatalysts (with varying Ni/Pd molar ratios in the range of ≈0.25–0.75) and the corresponding monometallic, Ni and Pd, analogues. Notably, the bimetallic Ni0.90Pd0.10 alloy nanocatalyst performed exceptionally well for the synthesis of biaryls by employing a wide range of substituted aryl halides and arylboronic acids having electron-donating and electron-withdrawing groups, and they exhibited high recyclability in water/ethanol solution at moderate reaction temperatures. Catalyst poisoning tests and leaching experiments inferred the heterogeneous nature of the Ni0.90Pd0.10 nanocatalysts. The significant synergistic interactions between Ni and Pd account for the observed high catalytic efficacy of the Ni0.90Pd0.10 nanocatalyst.