Schottky junctions have been widely applied to facilitate charge carrier separation through the formation of an internal electric field (IEF). However, the notably restricted spatial distribution of the IEF weakens the promotion of intrinsic carrier separation. In this study, we unveil that Au nanoparticles (NPs) in the Au/CuTCPP(Fe) Schottky junction can manipulate the spin polarization of CuTCPP(Fe) to inhibit inner carrier recombination. Experimental investigations and theoretical calculations reveal that the introduction of Au NPs leads to an increased population of spin-polarized electrons, effectively suppressing inner charge carrier recombination in CuTCPP(Fe) by employing the spin mismatch between spin-polarized photoexcited carriers. Moreover, as a typical active site for the oxygen reduction reaction, the oxygen adsorption configuration on spin-polarized Fe single-atom sites in Au/CuTCPP(Fe) is further optimized, resulting in boosted interfacial reactions. Leveraging the thiocholine-induced poisoning of the active sites and the magnetic-enhanced photoelectric response, Au/CuTCPP(Fe) is harnessed to develop a photoelectrochemical biosensing platform for organophosphorus pesticides. This work offers a promising method for manipulating the spin polarization of semiconductors in heterojunctions to mitigate intrinsic charge carrier recombination.