Carbon–nitride thin films were deposited by XeCl* ( λ=308 nm, τ FWHM≅30 ns) multipulse excimer laser irradiation of graphite targets in low-pressure (1–100 Pa) nitrogen atmosphere. We investigated the chemical bonding formation between the C and N atoms, and its influence upon the optical and mechanical properties of the obtained structures. We found that these properties strongly depend on the deposition parameters. These in turn determine the nitrogen content and the sp 3/sp 2/sp carbon atoms hybridization ratio of the synthesized material. According to our results, the increase of the nitrogen pressure or laser fluence in an attempt to obtain CN x thin films with higher N/C ratio does not lead to the formation of the theoretically predicted low-compressibility, high density, extremely hard β-C 3N 4 structure with the C atoms in the sp 3 hybridization state.