The development of transition metal intermetallic compounds, in which active sites are incorporated in lattice frameworks, has great potential for modulating the local structure and the electronic properties of active sites, and enhancing the catalytic activity and stability. Here we report that a new copper-based intermetallic electride catalyst, LaCu0.67Si1.33, in which Cu sites activated by anionic electrons with low work function are atomically dispersed in the lattice framework and affords selective hydrogenation of nitroarenes with above 40-times higher turnover frequencies (TOFs up to 5084 h-1) than well-studied metal-loaded catalysts. Kinetic analysis utilizing isotope effect reveals that the cleavage of the H-H bond is the rate-determining step. Surprisingly, the high carrier density and low work function (LWF) properties of LaCu0.67Si1.33 enable the activation of hydrogen molecules with extreme low activation energy (Ea = 14.8 kJ·mol-1). Furthermore, preferential adsorption of nitroarenes via a nitro group is achieved by high oxygen affinity of LaCu0.67Si1.33 surface, resulting in high chemoselectivity. The present efficient catalyst can further trigger the hydrogenation of other oxygen-containing functional groups such as aldehydes and ketones with high activities. These findings demonstrate that the transition metals incorporated in the specific lattice site function as catalytically active centers and surpass the conventional metal-loaded catalysts in activity and stability.