Heterostructures of two-dimensional transition metal dichalcogenides (TMD) have shown promise for various optoelectronic and novel valleytronic applications. Due to their type-II band alignment, photoexcited electrons and holes can separate into different layers through ultrafast charge transfer. While this charge-transfer process is critical for potential applications, the underlying mechanisms still remain elusive. Here, we demonstrate for a rotationally mismatched WSe2/MoSe2 heterostructure that directional ultrafast charge transfer between the layers becomes accessible by time-resolved optical second-harmonic generation. By tuning the photon energy of the pump pulse, one of the two materials is resonantly excited, whereas the polarization of the probe pulse can be optimized to selectively detect the charge transfer into the other material. This allows us to explore the interlayer hole transfer from the WSe2 into the MoSe2 layer and vice versa, which appears within a few hundred femtoseconds via hybridized intermediate states at the Γ-point. Our approach enables systematic investigations of the charge transfer in dependence of the rotational layer mismatch in TMD heterostructures.