The effect of nitrogen gas pressure on the atomic structure of Carbon Nitride (CN x ) thin films synthesized by pulsed laser deposition has been studied. CNx thin films were deposited from a graphite target in nitrogen atmosphere on silicon substrates at a temperature of 300 °C at laser fluences of 2 and 10 J/cm 2 , and at a gas pressure between 1 and 50 mTorr. The nitrogen to carbon (N/C) atomic ratio, bonding state, and microstructure of the deposited carbon nitride films were investigated by means of X-ray photoelectron (XPS), and Raman spectroscopy, respectively. Raman spectra show that the intensity ratio of the D peak over the G peak increases with increasing deposition gas pressure. XPS analysis revealed a strong dependence of the amount of structurally incorporated nitrogen upon the gas pressure; the increase of deposition gas pressure results in an increase in the N/C ratio. Further analyses of the XPS N Is core level spectra of the CN x films revealed a typical double peak arrangement, which is most pronounced for the highest laser fluence at low pressures. These two peak components indicate that the nitrogen bonded into a graphitic structure dominates over the two-fold coordinated pyridine-like bonding configuration. This favors the growth of intersecting corrugated graphene structures that may be considered to have a fullerene-like microstructure. The results were understood in combination with the optical emission of the plasma plume. It was found that the increase in pressure reduces the leading edge energies of the species in the plasma and increases the thermalization of the plasma due to a higher collision possibility.