Optical emission spectra ͑OES͒ from CH 4 /N 2 rf plasmas, which are used for the deposition of nitrogen-containing hydrogenated amorphous carbon ͑a-C:H:N͒ thin films, have been characterized. Previously unidentified spectral lines have been assigned to atomic N. Further identified species include CH, H, H 2 , N 2 , N 2 ϩ , N, and CN. Variations between spectra from the pure CH 4 or N 2 plasmas and the mixed CH 4 /N 2 plasma are discussed. The enhancement of excited nitrogen species, with the addition CH 4 , is attributed to Penning ionization. The observed OES variations of the CH 4 /N 2 plasma with power, pressure, and CH 4 /N 2 ratio are explained in terms of possible reaction mechanisms and their activation, and correlated with preliminary film growth characteristics.