Non-noble metal-based alloy catalysts are extensively utilized in diverse applications. Nevertheless, finding a suitable preparation strategy to precisely moderate the catalytic active site remains a substantial challenge and subsequently improves the atomic utilization and reaction efficiency. Herein, the non-noble trimetallic alloy catalysts (Ni3Ga0.8In0.2/SiO2) were fabricated by using the strategy of incorporating doping (Indium as doping metal) and modulating the Ni3Ga bimetallic alloy in which to precisely tune the electronic structure of catalysts. The dispersion of alloy nanoparticles on the support was investigated by HRTEM, alongside the valence and elemental distribution of the components by EDS, XRD, and XPS, demonstrating the successful alloying of the composite. Moreover, other metal-doped Ni-Ga-M/SiO2 (M=Cu, Pt) catalysts and Ni-Ga alloy were prepared and evaluated catalytic performance by the model reaction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). The experimental results revealed that suitable metal doping enhanced the reaction rate significantly, with the optimal effect of Indium among the different doping metals. Particular synergies arise from the homogeneous metals' similar atomic size and electronic structure. Theoretical calculations by Density Function Theory (DFT) have revealed that the doping of Indium resulted in electron transfer at the active interface of the catalyst, the gain of additional electrons by Ni, and the creation of electron vacancies at the active interface as a result of the electron deficiency of Ga and In, which enables the optimization of the catalytic reaction. In addition, the strategy can be extended to synthesize other trimetallic nanoparticle catalysts, which is expected to provide a new avenue for precise optimization and preparation of highly active non-precious metal catalysts.