Electrochemical water splitting has been highly recognized as a clean and sustainable method to produce hydrogen with high purity. An one-pot method to synthesize boron-doped RhFe alloy with excellent catalytic performance for hydrogen evolution is reported in the present work. Rhodium-Iron (RhFe) alloy nanoparticles, with diameter ranging from 1 to 5 nm, are distributed uniformly on the carbon support. The corresponding physicochemical and electrochemical results display that the sample of Rh:Fe = 2:1 post-treated at 200 degrees C (BRF21) shows the best performance for hydrogen evolution in 0.5 M H2SO4 aqueous solution; it exhibits good catalytic activity at a near zero onset potential. The required overpotential is found to be of about 25 mV at a current density of 10 mA cm(-2), which is 4 mV less than that of commercial Pt/C (29 mV); the Tafel slope is also comparable (32 mV dec(-1)) with Pt/C (30 mV dec(-1)). This work may provide a facile and environmentally friendly method to prepare B-doped catalysts with high electrochemical hydrogen evolution efficiency.