Summary: The generation of particles in a CH4/N2 radio‐frequency discharge has been studied in order to understand the effect of nitrogen incorporation into the particles. The nitrogen increase in the gas mixture leads to a modification of the particle behaviour in the plasma bulk. Moreover, for nitrogen ratios higher than 50%, changes in particle morphology and texture are observed. These modifications may be explained by the appearance of new radicals like CN evidenced, thanks to optical emission spectroscopy (OES). Moreover, the evolution of CH and CN emission lines has been studied. On the other hand, IR analyses have shown the presence of CN, NH, CH bonds in the particles and in the coatings. Their proportions depend on the nitrogen flow rate. A correlation between OES results and IR analyses has been established.