A comparison study of microstructure and bonds composition of carbon nitride (CN x ) films fabricated at atomic and ionic nitrogen source by pulse cathode arc method was presented. The relative fractions of CN/CC bonds, Nsp 3 C/Nsp 2 C and graphite-like/pyridine-like N bonding configurations in the CN films were evaluated by combining C1s and N1s X-ray photoelectron spectroscopy with the hardness and optical band gap measurement. The dependence of microstructure (quantity, size and disordering degree of Csp 2 clusters) of CN x films on the nitrogen source and pulse frequency was determined by Raman spectroscopy. Films with high atomic ratio of nitrogen/carbon (0.17) and high hardness were produced at ionic nitrogen source and low pulse frequency. The results showed that ionic nitrogen source facilitated the formation of CN bonds and Nsp 2 C bonding configurations (mainly in graphite-like N form). Moreover presenting an optimum pulse frequency (∼10Hz) leaded to the most nitrogen coordinated with sp 3 -C and the highest ratio of CN/CC bonds in the CN x films. An equilibrium action mechanism might exist between the quantity and energy of carbon and nitrogen ions/atoms, giving more nitrogen-incorporated carbon materials. These allow us to obtain the high content of NCsp 3 bonding and expected bonding structure by optimizing pulse frequency and nitrogen source.