Ultraviolet photoelectron spectroscopy was used to study energy levels of (0001) and (000 (1) over bar) surfaces of bare CdS crystal terminated with Cd and S atoms, respectively, as well as energy level alignment at hybrid interfaces of CdS crystal and donor zinc phthalocyanine (PcZn) or acceptor fluoro-substituted zinc phtalocyanine (F-PcZn) layers, respectively. The data allowed us to distinguish a slight difference between ionization potential of the Cd- and S-terminated facets of the crystal and different contribution of these surfaces to formation of the interfacial dipole at the hybrid interfaces. Ionization potential for the 5 terminated surface was slightly higher as compared to the Cd-terminated one for the same crystal, and a more, positive dipole was always created on the S-terminated surface independent of whether the donor or acceptor phthalocyanine was used. The results showed that PcZn and F-PcZn render a dual effect at the CdS surface. First, the molecules created a dipole at the interface, however, the sign of this dipole was opposite for PcZn and F-PcZn, respectively. Second, the both molecules contributed to the formation of a depletion layer near the crystal surface. The role of the surface states of the crystal in the above effects has been elucidated. Interaction of PcZn and CdS surface was associated with the pinning of the upper occupied level of the surface states to the positive charge transfer state corresponding to the oxidized HOMO level of the molecule at the interface, whereas interaction of F-PcZn and CdS surface with the pinning of the upper occupied level of the surface states to the negative charge transfer corresponding to the reduced LUMO level of the molecule at the interface, i.e., similar to what is observed for the metal organic interfaces, where an upper occupied level of semiconductor surface states in our case plays the role of Fermi level in metal. (C) 2017 Elsevier B.V. All rights reserved.