Metal deposition on a p-sexiphenyl (6P) film was studied by ultraviolet photoelectron spectroscopy (UPS), metastable atom electron spectroscopy (MAES), and X-ray photoelectron spectroscopy (XPS). The deposited metals were Au, Mg, and several alkali metals (K, Na, Rb, and Cs). No chemical reaction between 6P and Au or Mg was observed in the measured spectra, while additional gap states appeared in the UPS and MAES spectra by deposition of the alkali metals. The diffusion of Au and Mg atoms into the 6P film was observed in the MAES spectra. We found the trend of the vacuum level shift is different between the systems of the 6P on the Au and its reversed systems (Au on the 6P film), suggesting the different formation of the interface depending on the deposition sequence.