Bimetallic catalysts hold great expectations for high catalytic performance, typically, due to the geometric and electronic interactions between metal and promoter on the catalyst. This work is committed to developing a bimetallic catalyst that incorporates uniform Pd and Mo carbide for selective hydrogenation. By adding SiO2 templates to glucose-metal cation complexation, which etched after carbonization, a unique hierarchical mesoporous carbon can be synthesized in which uniformly distributed Pd nanoparticles interact with Mo2C deposited in the vicinity. The porous PdMo2C/C catalyst is used for the selective hydrogenation of nitroaromatics and found to achieve full conversion at room temperature in 25 min, which shows significantly higher turnover frequencies (TOFs) as compared with porous Mo2C/C and Pd/C. This activity enhancement contributed to the electronic interaction between Mo2C and Pd particles, resulting in a promotive effect on H-2 activation. The PdMo2C/C catalyst presents a stable recycling performance for the hydrogenation of nitrobenzene. We believe that these findings can be easily extended to produce other metal-carbide-based hierarchical porous carbon catalysts for various advanced applications.