Copper polyphthalocyanine (CuPPC), a 2D conjugated polymer, is a promising material for electronics and photovoltaics, but its applications were hindered by a poor processability. We propose an experimental approach, by which thin films of CuPPC, can be directly synthesized in a chemical vapor deposition (CVD) set-up at mild temperature (420 degrees C). High polymerization degree and high crystallinity of the films were confirmed by TEM, FTIR and UV-vis studies. From XRD and TEM electron diffraction, we conclude that the polymer has AA layer stacking with the inter-layer distance of 0.32 nm. The assignment of X-ray and TEM diffraction patterns was based on quantum-chemical calculations. Based on the latter, we also discuss electronic structure and conclude that CuPPC is rather a semi-metal than semi-conductor. (c) 2013 Elsevier Ltd. All rights reserved.