Developing new anode materials to meet the high-energy demands of the next generation of rechargeable lithium-ion batteries (LIBs) is still a challenging work. In this work, hierarchically porous Mo2C-C (HP-Mo2C-C) hybrid has been designed and synthesized by a freeze-drying-assisted route. The resultant HP-Mo2C-C hybrid has a surface area as high as 200.6m2 g−1. When evaluated as an anode material for LIBs, the HP-Mo2C-C hybrid displays excellent lithium storage performance in terms of specific capacity, cycling stability and rate capability. The pore engineering and hybridization with carbon are believed to be responsible for the significantly improved electrochemical performance. The novel interconnected pore structure allows for easy diffusion of the electrolyte and at the same time can enhance the HP-Mo2C-C/electrolyte contact area, shorten the Li+ diffusion length, and accommodate the strain induced by the volume change during the electrochemical reaction. Moreover, the hybridization with carbon could largely improve the conductivity of the electrode.