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An interfacial structure is crucial to the photoinduced electron transport for a heterostructure photocatalyst. Constructing an interfacial electron channel with an optimized interfacial structure can efficiently improve the electron-transfer efficiency. Herein, the rapid electron-transfer channels were built up in a Cu 2 O/SrFe 0.5 Ta 0.5 O 3 heterojunction (Cu 2 O/SFTO) based on the selective bonding effect of heterologous surface oxygen vacancies in the SFTO component. The heterologous surface oxygen vacancies, namely, V O-Fe and V O-Ta , respectively, adjacent to Fe and Ta atoms, were introduced into fabricating the Z-scheme Cu 2 O/SFTO heterojunction. Compared with sample Cu 2 O/SFTO with V O-Fe , the photocatalytic NO removal efficiency of sample Cu 2 O/SFTO with V O-Fe and V O-Ta was increased by 22.5%. The enhanced photocatalytic performance originated from the selective bonding effect of heterologous V O-Fe and V O-Ta on the interfacial electron-separating and -transfer efficiency. V O-Fe is the main body to construct the interfacial electron-transfer channels by forming interfacial Fe-O-Cu(I) bonds, which causes lattice distortion at the interface, and V O-Ta can optimize the structure of interfacial channels by balancing the electron density of SFTO to control the average space of the interface transition zone. This research provides a new cognitive perspective for constructing double perovskite oxide-based heterostructure photocatalysts.