Developing novel and high performance electrocatalysts for use in hydrogen evolution reactions (HER) as substitutes for noble metal based electrocatalysts is imperative and, so far, has been a challenge. Herein, a self-supported Cu3P/Ni2P hybrid on nickel foam (Cu3P/Ni2P@NF) is prepared by a simple galvanic replacement reaction coupled with phosphorization. Subsequently, Cu3P/Ni2P@NF is modified by conducting cyclic voltammetry scans in 0.5 M H2SO4 solution. Interestingly, after electrochemical tuning, the as-prepared Cu3P/Ni2P@NF exhibits significantly enhanced HER activity. Particularly, the resultant Cu3P/Ni2P@NF catalyst after 4000 cycles exhibits superior catalytic activity and long-term stability for HER with an overpotential of only 67 mV at the current density of 10 mA cm-2, and a low Tafel slope of 43.9 mV dec-1. The improved HER performance is attributed to the increased intrinsic activity of the Cu3P/Ni2P@NF with its optimized crystal and electronic structure, as well as an increased number of accessible active sites due to surface dissolution and recrystallization induced by electrochemical modification.