16 nm thick Copper Phthalocyanine (CuPc) films were deposited at room temperature in Ultra High Vacuum onto "n" and "p" type doped Si(111) substrates covered with a native SiO(2) overlayer. Atomic Force Microscopy indicates that the two substrates are both atomically flat (0.15 nm root mean square roughness). Angle dependent X-ray photoemission spectroscopy shows that the thickness of the native SiO(2) over-layer is 0.8 nm (both for the "n" and "p" type Si substrate). Despite the identity of the substrate roughness, of the SiO(2) thickness, and of the CuPc film growth conditions, the organic films (made out of crystallites in the alpha-phase, as checked with X-ray Diffraction) grown on the "p" and "n" type substrate show clearly different morphological features (determined with Atomic Force Microscopy and Scanning Electron Microscopy measurements). While the CuPc film on "p" Si(111) shows a compact network of densely packed crystallites with sizes (along the substrate plane) ranging from 50 to 100 nm, the CuPc film on "n" Si(111) shows a slightly more open network of larger crystallites (with 75-150 nm size range). Accordingly, the CuPc film roughness is 0.67 nm and 1.15 nm for the "p" and "n" type substrate respectively. Due to the increased surface to volume effects (lower crystallite size) affecting the CuPc film on "p" Si(111), this film exhibits stronger interaction with oxygen and water vapor of the ambient air, as determined by photoemission spectroscopy experiments performed on samples as grown "in situ" and after prolonged (1 year) exposure to air. (C) 2008 Elsevier B.V. All rights reserved.