The circumstances of transferred electrons across organic/inorganic interfaces have attracted intensive interest because of the distinctive electronic structure properties of those two components. Leveraging ab initio nonadiabatic molecular dynamics methods in conjunction with spin dynamics induced by spin-orbital couplings (SOCs), this study reports two competitive channels during photoinduced dynamical processes in the prototypical ZnPc/monolayer MoS 2 heterojunction. Interestingly, the electron-transfer and relaxation processes occur simultaneously because of the enhancement of electron-phonon couplings and expansion of dynamical pathways by SOCs, suggesting that the electron-transfer rate and relaxation processes can be tuned by SOCs, hence yielding the performance promotion of photovoltaic and photocatalytic devices. Additionally, approximately half of the transferred electrons flip their spin within 1.6 ps because of strong SOCs in MoS 2 , achieving great agreement with experimental measurements. This investigation provides instructive perspectives for designing novel devices and applications based on organic/inorganic heterojunctions, demonstrating the importance of spin dynamics simulations in exploring sophisticated photoinduced processes in materials.