We developed a molybdenum (Mo)‐doped cobalt (Co)‐heterostructure embedded on a phosphorous (P) and nitrogen (N) dual‐doped porous carbon which exhibits an intrinsic electronic transport channel of Co to Mo and P. The P,Mo,O‐Co/PNC/NF (NF = Nickel foam) electrode offers 335 mV overpotential at 10 mA cm‐2 in OER as compared with PMA‐ZIF67‐NC/NF and ZIF67‐NC/NF electrode with an overpotential of 357 and 373 mV respectively. Linear sweep voltammetry (LSV) of overall water splitting (OWS) supports that the current density gradually increased at a cell potential of 1.6 V with a maximum of 40 mA with a corresponding cell potential of 1.79 V at a current density of 10 mA cm−2. Density functional theory (DFT) calculations for water adsorption on optimized [111] surface of Co, CoMo, and CoMoP2 with adsorbed H2O and corresponding lattice determine the electron density difference of [111] surface with adsorbed H2O for Eads (eV) 4.23 corresponds to adsorption energy for CoMoP2. XANE‐EXAFS spectroscopy of P,Mo,O‐Co/PNC at Co K edge and Mo K edge suggests the presence of higher valence of both Cox+ and Mox+ without metallic Co and Mo and Co‐P and Mo‐P bonds as major structural units due to phosphidation as determined by R‐space FT‐EXAFS spectra.