An understanding of the surface and interface states of the organic material and the underlying andoe material is meaningful for organic light-emitting devices (OLEDs). The 8-Hydroxyquinolinolatolithium (Liq) was deposited on indium-tin-oxide (ITO) coated glass by traditional vacuum evaporation.The thickness of Liq is about 120nm. The morphology, surface and interface electron states of the Liq and the underlying ITO have been investigated with the utilization of the atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) technology. AFM observation indicated that Liq grows in the shape of an asymmetrically-distributed island, with each island resembling a round hillock and different size. The Liq film is not very uniform and teemed with many pinholes and cracks.The analysis on XPS spectra of the surface of the Liq/ITO samples shows that, the core-levels of Li1s, C1s, N1s, O1s, In3d5/2, and Sn3d5/2, spectra slightly shift towards lower binding energy with the increase of the sputtering time, which may be caused by the effect of oxygen, indium and tin in ITO diffusing into Liq layer and the argon ions beam with energy. Coordination bond between Li atoms and N atoms does not exist in Liq, which is the main reason why Liq is the blue electroluminescent material. The C atoms mainly bond to C, N and O atoms, forming C-C, C-N=C and C-O bonds, respectively. And there is a speculation of the existence of contaminated C atoms in the surface of ITO, while the O atoms basically originate from quinolate rings and the absorption of O2 and H2O. At the interface N and O, In and Sn interact to some extent, which probably affects the emitting colour of Liq based OLEDs. The analysis of surface of In3d and Sn3d spectrum by XPS provides additional evidence of the existence of cracks and pinholes in Liq layer, leading to much absorption of air molecules.