Abstract Organic–metal and organic–organic interfaces account for the functionality of virtually all organic optoelectronic applications and the energy-level alignment is of particular importance for device performance. Often the energy-level alignment is simply estimated by metal work functions and ionization energies and electron affinities of the organic materials. However, various interfacial effects such as push back, mirror forces (also known as screening), electronic polarization or charge transfer affect the energy-level alignment. We perform x-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) measurements on copper-hexadecafluorophthalocyanine (F₁₆CuPc) and titanyl-phthalocyanine (TiOPc) thin films on Ag(111) and use TiOPc bilayers to decouple F₁₆CuPc layers from the metal substrate. Even for our structurally well-characterized model interfaces and by stepwise preparation of vacuum-sublimed samples, a precise assignment of vacuum-level and energy-level shifts remains challenging. Nevertheless, our results provide guidelines for the interpretation of XPS and UPS data of organic–metal and organic–organic interfaces.