In this work, we report on a structural and compositional characterization of B–C–N thin films deposited by laser reactive ablation of a B 4 C target, in low-pressure (5 Pa) nitrogen atmosphere. For target ablation, a KrF excimer laser (λ=248 nm, τ=20 ns) has been used, at the fluences of 6 and 12 J/cm 2 . Films have been deposited on silicon 〈100〉 substrates at room temperature. Scanning electron miroscopy (SEM), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and Fourier transform-infrared spectroscopy (FT-IR) characterization techniques were used to analyze the composition and the structure of the deposited films. The film results to be a mixture of sp 2 /sp 3 BN and sp 2 /sp 3 nitrogenated C phases. The concentration of the different BN phases depends on the used laser fluence for the deposition of the film.