A neutral molecular radical, lithium phthalocyanine (LiPc), was synthesized by electrochemical oxidation of dilithium phthalocyanine. The synthesized LiPc exhibited very narrow paramagnetic resonance signals due to delocalization of the unpaired spin in the pi -conjugating Pc macrocycle. Thin films of LiPc were prepared by vapor-deposition onto the (100) surface, of alkali halide substrates such as KCl, KBr and KI. Transmission electron microscopy and electron diffraction investigations elucidated that epitaxially oriented thin layer of the X-form LiPc was obtained only when deposited on the KCl substrate kept at 150 degreesC. Perfect lattice-matching. between the tetragonal ab-plane of the LiPc crystal and the KCl ionic surface. resulted in the root 10 X root 10 type of epitaxy. This epitaxial nucleation enabled the LiPc molecules to adsorb at the most stable sites of the KCl ionic lattice holding their molecular planes parallel to the KCl (100) surface. Otherwise, on the KBr and KI substrates, the LiPc molecules crystallized in island-like grains of the a-form phase taking various orientations on the surface. Preliminary study by magnetic force microscopy of the LiPc film suggested different magnetic ordering in such epitaxial thin layers of the X-form and island-like grains of the a-form.