We have used photoelectron spectroscopy to determine the energy-level alignment at organic heterojunctions made of manganese phthalocyanine (MnPc) and the fullerene C₆₀. We show that this energy-level alignment depends upon the preparation sequence, which is explained by different molecular orientations. Moreover, our results demonstrate that MnPc/C₆₀ interfaces are hardly suited for application in organic photovoltaic devices, since the energy difference of the two lowest unoccupied molecular orbitals (LUMOs) is rather small.