Plasma catalysis offers a flexible and decentralized solution for CO₂ hydrogenation to methanol under ambient conditions, avoiding the high temperatures and pressures required for thermal catalysis. However, the reaction mechanism, particularly plasma-assisted surface reactions, remains unclear, limiting the development of efficient catalysts for selective methanol synthesis. Here, we report a bimetallic Ni-Co catalyst effective in plasma-catalytic CO₂ hydrogenation to methanol at 35°C and 0.1 MPa, achieving 46% methanol selectivity and 24% CO₂ conversion. In situ plasma-coupled Fourier transform infrared characterization, along with density functional theory calculations, reveals that the engineered bimetallic sites act as primary active centers for methanol synthesis, promoting the rate-determining step in H-radical-induced reaction pathways by reducing steric hindrance effects. This work demonstrates the significant potential of bimetallic catalysts in plasma-catalytic CO₂ hydrogenation to methanol under ambient conditions, representing a major step toward sustainable CO₂ conversion and fuel production.