A promising strategy toward ultrathin, sensitive photodetectors is the combination of a photoactive semiconducting transition-metal dichalcogenide (TMDC) monolayer like MoS₂ with highly conductive graphene. Such devices often exhibit a complex and contradictory photoresponse as incident light can trigger both photoconductivity and photoinduced desorption of molecules from the surface. Here, we use metal–organic chemical vapor deposition (MOCVD) to directly grow MoS₂ on top of graphene that is deposited on a sapphire wafer via chemical vapor deposition (CVD) for realizing graphene–MoS₂ photodetectors. Two-color optical pump–electrical probe experiments allow for separation of light-induced carrier transfer across the graphene–MoS₂ heterointerface from adsorbate-induced effects. We demonstrate that adsorbates strongly modify both magnitude and sign of the photoconductivity. This is attributed to a change of the graphene doping from p- to n-type in case adsorbates are being desorbed, while in either case, photogenerated electrons are transferred from MoS₂ to graphene. This nondestructive probing method sheds light on the charge carrier transfer mechanisms and the role of adsorbates in two-dimensional (2D) heterostructure photodetectors.