Efficient electrocatalyst materials for several applications, including energy storage and conversion, have become vital for achieving technological progress. In this work, a CoO@Co3O4/C composite with abundant oxygen vacancies was successfully synthesized. The concentration of the oxygen vacancies was well controlled by changing the degree of vacuum during the heat treatment and was characterized by XPS and EPR. The existence of the porous structure arising from the cobalt oxide particles embedded in the carbon matrix provided an efficient charge and gas transmission path, significantly improving the performance of electrocatalytic oxygen evolution. Sufficient reactive sites were provided from both the oxygen vacancies and the heterogeneous interface. The mechanism of enhanced OER originating from the built-in electric field derived from oxygen vacancies was investigated. Consequently, the CoO@Co3O4/C composites offered an OER overpotential of 287 mV at a current density of 10 mA cm-2 with good stability in 1 mol L-1 KOH. In addition, combined with surface photovoltage (SPV), transient photovoltage (TPV), DFT, and in situ Raman spectroscopy, the effect of oxygen defects on the electron migration ability and transformation of the intermediate products were investigated to further understand the nature of catalytic activity in OER.