Penning ionization electron spectroscopy and ultraviolet photoelectron spectroscopy were used to characterize ultrathin films (one to several monolayers) of chloroaluminum phthalocyanine during layer-by-layer vacuum deposition onto a graphite substrate. At one monolayer, molecules deposited on the substrate held at room temperature are oriented flat to the substrate with the chlorine atom protruding outside the film surface. With increasing film thickness, molecules are gradually tilted in subsequent layers. The monolayer film deposited on the substrate at -170 degrees C shows a disordered molecular arrangement (tilted molecules), but the change in the arrangement, disordered (tilted) to ordered (flat), is observed upon heating the film up to 100 degrees C.