In the face of hydrogen society, considerable efforts to develop highly active and stable electrocatalysts for hydrogen evolution reaction (HER) have been undertaken to realize sustainable hydrogen production using water splitting. A rational design of mesoporous structure is considered as a promising approach for efficient electrochemical reaction. Herein, we demonstrate the mesoporous rhodium nanoparticles (MRNs) synthesized by simple chemical reduction using polymeric micelle template for the high electrocatalytic performance of HER in an acidic media. Due to the large accessible surface area and abundant low-coordinated atoms on the concave pore surface, our MRNs exhibits the lower overpotential of 29.4 mV at a current density of 10 mA/cm² for HER, compared to 33.8 mV of Rh black. The MRNs also achieves a small Tafel slope of 30.9 mV/dec, enhanced exchange current density and excellent stability in long-term operation. These kinetic and stability properties are attributed to the uniform mesoporous morphology and the robust structure of the MRNs.