Van der Waals heterostructures consisting of graphene and transition metal dichalcogenides have shown great promise for optoelectronic applications. However, an in-depth understanding of the critical processes for device operation, namely, interfacial charge transfer (CT) and recombination, has so far remained elusive. Here, we investigate these processes in graphene-WS₂ heterostructures by complementarily probing the ultrafast terahertz photoconductivity in graphene and the transient absorption dynamics in WS₂ following photoexcitation. We observe that separated charges in the heterostructure following CT live extremely long: beyond 1 ns, in contrast to ~1 ps charge separation reported in previous studies. This leads to efficient photogating of graphene. Furthermore, for the CT process across graphene-WS₂ interfaces, we find that it occurs via photo-thermionic emission for sub-A-exciton excitations and direct hole transfer from WS₂ to the valence band of graphene for above-A-exciton excitations. These findings provide insights to further optimize the performance of optoelectronic devices, in particular photodetection.