Penning ionization electron spectroscopy (PIES) and ultraviolet photoelectron spectroscopy (UPS) were used to characterize ultrathin films (0.2-3 MLE) of titanyl phthalocyanine (OTiPc) deposited on a graphite substrate. The change in the molecular orientation at the outermost surface layer was selectively probed by PIES during the variations of the thickness and temperature of the films.