The H2 production using N2H4 splitting (OHzS) was often constrained by the requirement for insufficient stability, distinct catalysts at the anode and cathode, and the high-cost electrocatalyst associated with confined activity. This work verified the efficacy of surfactant-free branched CuAu nano-alloy as a bifunctional electrocatalyst for H2 production. Benefiting from its favorable electronic structure and surfactant-free surface, surfactant-free CuAu nano-alloy demonstrated a reduced over-potential compared withpure Cu, pure Au, and CuAu nano-alloy prepared by surfactant. When using branched CuAu nano-alloy as both cathodic and anodic electrodes, a cell voltage of 0.768V was required to drive a current density of 10mA/cm2. After 2550min of H2 generation, the amplitude of the working potential for anodic reactions was found to be less than 0.92%. The enhanced electrocatalytic activity could be also applied to H2O2 and NaNO2 sensors. The CuAu nano-alloy exhibited a 2.35-folds increase in sensitivity compared to pure Au nano-crystals in the detection of H2O2. Moreover, the detection of NaNO2 in water solution has been successfully achieved. The detection range 0-175.0mM was much wider than that ofsensors in previous works.