AbstractWhen a molecule interacts chemically with a metal surface, the orbitals of the molecule hybridise with metal states to form the new eigenstates of the coupled system. Spatial overlap and energy matching are determining parameters of the hybridisation. However, since every molecular orbital does not only have a characteristic spatial shape, but also a specific momentum distribution, one may additionally expect a momentum matching condition; after all, each hybridising wave function of the metal has a defined wave vector, too. Here, we report photoemission orbital tomography measurements of hybrid orbitals that emerge from molecular orbitals at a molecule-on-metal interface. We find that in the hybrid orbitals only those partial waves of the original orbital survive which match the metal band structure. Moreover, we find that the conversion of the metal’s surface state into a hybrid interface state is also governed by momentum matching constraints. Our experiments demonstrate the possibility to measure hybridisation momentum-selectively, thereby enabling deep insights into the complicated interplay of bulk states, surface states, and molecular orbitals in the formation of the electronic interface structure at molecule-on-metal hybrid interfaces.