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The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is a key performance-limiting step of rechargeable zinc-air batteries. Developing a reliable strategy to optimize the activity of Co occupied the tetrahedral site (Co th) is crucial for enhancing electrocatalytic performance and still needs further elaborate elucidation. Here, Mo dopants were used as electron donors to construct low-valence Co th sites in cobalt phosphide, resulting in downshifted d -band centers and strengthened hybridization between Co 3 d and P 3 p orbitals. The negative charges are easier to accumulate on three antibonding orbitals of Co th , promoting the desorption of oxygen intermediates, as evidenced using density functional theory calculations and in-situ spectroscopic investigations. The optimal catalyst delivers impressive ORR and OER performance, in terms of half-wave potential of 0.84 V for ORR and overpotential of 247 mV for OER. In general, this work opens a new opportunity to rationally regulate electronic structure of Co th sites via introducing an electron donor, as well as provides guidance for exploring electronic descriptors of tetrahedral sites. [Display omitted] • A well-managed electronic structure was established via electron-donors Mo doing. • The electron-rich environments optimize active site-intermediate interactions. • The Mo-Co 2 P@PNC shows excellent ORR activity and good stability. • The Mo-Co 2 P@NPC-based ZAB exhibits a high peak power density of 185 mW cm−2. [ABSTRACT FROM AUTHOR]