We use time- and angle-resolved photoemission spectroscopy (tr-ARPES) to investigate ultrafast charge transfer in an epitaxial heterostructure made of monolayer WS$_2$ and graphene. This heterostructure combines the benefits of a direct gap semiconductor with strong spin-orbit coupling and strong light-matter interaction with those of a semimetal hosting massless carriers with extremely high mobility and long spin lifetimes. We find that, after photoexcitation at resonance to the A-exciton in WS$_2$, the photoexcited holes rapidly transfer into the graphene layer while the photoexcited electrons remain in the WS$_2$ layer. The resulting charge transfer state is found to have a lifetime of $sim1$,ps. We attribute our findings to differences in scattering phase space caused by the relative alignment of WS$_2$ and graphene bands as revealed by high resolution ARPES. In combination with spin-selective excitation using circularly polarized light the investigated WS$_2$/graphene heterostructure might provide a new platform for efficient optical spin injection into graphene.
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