Thin layers X-ray diffraction study technique utilizing single-crystal X-ray diffractometer equipped with microfocus X-ray tube is described. It is shown that the layers of the tetra-fluorinated cobalt phthalocyanine (CoPcF4), deposited by thermal evaporation in vacuum on a polished surface of the substrate (glass, quartz), have a highly oriented polycrystalline structure. All the crystallites have the (00l) plane oriented along the surface of the substrate. CoPcF4 X-ray diffraction pattern indexing was conducted and unit cell parameters were determined. It is shown that crystal phase of both polycrystalline powder and thin layers of CoPcF4 are isostructural to that of α-CoPc.