We present ultraviolet photoelectron spectroscopy studies on alkali metal-intercalated thin films of electroluminescent p-sexiphenyl (6P) and the organic hole transporting material N,N'-bis-(1-naphthyl)-N,N'-diphenyll-1,1-biphenyl1-4,4'-diamine (alpha-NPD). The formation of new occupied electronic states in the otherwise empty energy gap of 6P and alpha-NPD is observed, accompanied by a significant shift of the Fermi-level. Depending on the work function phi of the substrate used for the organic thin films, we observe two different scenarios at low intercalation levels: the new electronic states are observed at (and even above) E-F for high phi substrates, whereas they are observed below E-F for low phi substrates. At high intercalation levels, all the states are observed below E-F. The observation of states at and above E-F is attributed to a lack of thermodynamic equilibrium across the organic thin film. (c) 2005 Elsevier B.V. All rights reserved.