Low temperature scanning tunneling microscopy (LT-STM) and scanning tunneling spectroscopy (STS) have been used to investigate adsorbed copper phthalocyanine (C32H16N8Cu) molecules on an ordered ultrathin Al2O3 film on the Ni3Al( 1 1 1) surface as a function of coverage and annealing temperature. For sub-monolayer coverage and a deposition temperature of 140 K two different planar molecular adsorption configurations rotated by 308 with respect to each other were observed with submolecular resolution in the STM images. The template effect of the underlying oxide film on the CuPc orientation, however, is only weak and negligible at higher coverages. For theta(CuPc)approximate to 1 ML, before completion of the first layer, the growth of a second layer was already observed. The measured spacing of 3.5 A S between first and second layer corresponds to the distance between the layers in the alpha-modification of crystalline CuPc. The molecules deposited at 140 K are thermally stable upon prolonged annealing to temperatures up to 250 K. By the use of STS the lowest unoccupied molecular orbital ( LUMO) of the adsorbed copper phthalocyanine molecules has been identified at an energy of 1.2 eVabove E-F. The lateral distribution of the electronic states of the CuPc has been analyzed and mapped by STS. (c) 2008 Elsevier B. V. All rights reserved.