Thedevelopment of electrocatalysts withlow cost, high efficiency, and long-term durability is crucial for advancing green hydrogen production.Transition metal phosphides (TMPs) have been proved to be efficient electrocatalyst, while the improvement in the performance and durability of the TMPs remains a big challenge.Employing atmospheric pressure chemical vapor deposition (APCVD) and phosphorization, FeP/Ti electrodes are fabricated featuring controllable oxygen ingredients (O-FeP/Ti). This manipulation of oxygen content fine-tunes the electronic structure of the catalyst, resulting in improved surface reaction kinetics and catalytic activity.The optimized O-FeP-400/Ti exhibits outstanding HER activity with overpotentials of 142 and 159 mV at -10 mA cm-2in 0.5 M H2SO4and 1 M KOH, respectively.Notably, the obtained O-FeP/Ti cathode also displays remarkable durability of up to 200 h in acidic electrolyte withsurface topographyremaining intact.For the first time, the low-valence titanium oxide (Ti3O) interlayeris identified in the composite electrode and ascribed for the superior connection between Ti substrate and the surface O-FeP catalyst, as supported by experimental resultsand density functional theory (DFT) analysis.This work has expanded the potential applicationsof transition metal phosphides (TMPs) as a cost-effective, highly efficient and durable catalyst for water splitting.