Two-dimensional transition-metal dichalcogenides (TMD) can be combined with other materials such as organic small molecules to form hybrid van der Waals heterostructures. Because of different properties possessed by these two materials, the hybrid interface can exhibit properties that cannot be found in either of the materials. In this work, the zinc phthalocyanine (ZnPc)–molybdenum disulfide (MoS₂) interface is used as a model system to study the charge transfer at these interfaces. It is found that the optically excited singlet exciton in ZnPc transfers its electron to MoS₂ in 80 fs after photoexcitation to form a charge transfer exciton. However, back electron transfer occurs on the time scale of ∼1–100 ps, which results in the formation of a triplet exciton in the ZnPc layer. This relatively fast singlet–triplet transition is feasible because of the large singlet–triplet splitting in organic materials and the strong spin–orbit coupling in TMD crystals. The back electron transfer would reduce the yield of free carrier generation at the heterojunction if it is not avoided. On the other hand, the spin-selective back electron transfer could be used to manipulate electron spin in hybrid electronic devices.