Developing heterogeneous catalysts for hydrogenation under mild conditions is industrially significant, but there still remain some challenges in the preparation of inexpensive and highly active catalysts. Herein, we present Co-MoxC catalysts prepared by a one-pot pyrolysis method for which excellent catalytic performance toward selective hydrogenation is achieved. The highest turnover frequency (TOF) of nitrobenzene hydrogenation reached up to 105.3 h(-1) with a selectivity of higher than 99% at 60 degrees C. As evidenced by our experiment and analysis, the electronic structure of cobalt can be affected by the in situ-formed molybdenum carbide, which led to an improved dispersion via the interaction between Co and MoxC as well as advanced catalytic performance. These results could provide some potential for the design of efficient hydrogenation catalysts for further industrial applications.