The molecule/metal interface is the key element in charge injection devices. It can be generally defined by a monolayer-thick blend of donor and/or acceptor molecules in contact with a metal surface. Energy barriers for electron and hole injection are determined by the offset from HOMO (highest occupied) and LUMO (lowest unoccupied) molecular levels of this contact layer with respect to the Fermi level of the metal electrode. However, the HOMO and LUMO alignment is not easy to elucidate in complex multicomponent, molecule/metal systems. We demonstrate that core-level photoemission from donor-acceptor/metal interfaces can be used to straightforwardly and transparently assess molecular-level alignment. Systematic experiments in a variety of systems show characteristic binding energy shifts in core levels as a function of molecular donor/acceptor ratio, irrespective of the molecule or the metal. Such shifts reveal how the level alignment at the molecule/metal interface varies as a function of the donor-acceptor stoichiometry in the contact blend.