Rational design of highly efficient noble-metal-unbound electrodes for hydrogen and oxygen production at increased current density is crucial for robust water-splitting. A facile hydrothermal and room-temperature aging method is presented, followed by chemical vapor deposition (CVD), to create a self-sacrificed hybrid heterostructure electrocatalyst. This hybrid material, (Mn-(Co,Ni)2P/CoP/(N,S)-C), comprises manganese-doped cobalt nickel phosphide (Mn-(Co,Ni)2P) nanofeathers and cobalt phosphide (CoP) nanocubes embedded in a nitrogen and sulfur co-doped carbon matrix (N,S)-C on nickel foam. The catalyst exhibits excellent performance in both the hydrogen evolution reaction (HER; η10 = 61mV) and oxygen evolution reaction (OER; η10 = 213mV) due to abundant active sites, high porosity, and enhanced hetero-interface interaction between Mn-(Co2P-Ni2P) CoP, and (N,S)-C supported by significant synergistic effects observed among different phases through density functional theory (DFT) calculations. Impressively, (Mn-(Co,Ni)2P/CoP/(N,S)-C (+,-) shows an extra low cell voltage of 1.49 V@10mA cm-2. Moreover, the catalyst exhibits remarkable stability at 100 and 300mA cm-2 when operating as a single stack cell electrolyzer. The superior electrochemical activity is attributed to the enhanced electrode-electrolyte interface among the multiple phases of the hybrid structure.