[en] The unoccupied electronic structure of stacked layers of copper(II)phthalocyanine (CuPc) and perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) on Ag(1 1 1) has been investigated by means of two-photon photoemission (2PPE). We find a rich electronic structure comprising at least five unoccupied electronic states which we identify based on their energetic position and their dispersion in momentum space. More specifically, we observe the first and the second image-potential states of the modified Ag(1 1 1) surface, as well as the metal–organic interface state (IS) inherent to the PTCDA/Ag(1 1 1) interface. Moreover, two additional molecular features are observed for the CuPc/PTCDA/Ag(1 1 1) system which we attribute to an unoccupied molecular orbital (LUMO  +  2) of CuPc. The 2PPE intensity of the IS exhibits a pronounced dependence on the pump photon energy, which closely follows the optical absorption of the outer molecular layer. This strongly points to charge transfer from the optically excited molecules to the interface state. (paper)