The development of durable, efficient catalysts is vital in electrochemical water dissociation. Metal-organic frameworks (MOFs) based nanomaterials have been explored due to their well-distribution metal nodes and stability, but the shortage of efficient cathode compounds for electrochemical hydrogen evolving restricted their industrial applications. Herein, CuSe nanocrystals embedded in the octahedral carbon frameworks (CuSe/C) were fabricated using a copper-related MOF template through a one-step selenization technique. Interestingly, the catalytic efficacy of CuSe/C is better than that of Cu/C and Cu-MOF as catalysts for hydrogen generation in an acidic medium. In particular, CuSe/C shows a moderate overpotential of 220 mV at a current density of 10 mA cm and a low Tafel slope of 54.5 mV dec. Also, this catalyst presents outstanding durability with 2000 cycling operations and 12 h of testing by chronoamperometry. The high efficiency is assigned to the synergistic effect of CuSe nanoparticles and carbon frameworks, which play essential roles in increasing exposed catalytic sites and protected active centers. The results may open potential direction to prepare economical hydrogen-evolving electrocatalysts.