A simple collisional–radiative model for argon and xenon is used, in conjunction with optical emission spectroscopy (line-ratio technique), to determine the electron temperature and electron density in low-pressure discharges containing argon and xenon. Satisfactory agreement is obtained between this method and the Langmuir probe for an inductively coupled plasma containing neon, argon and xenon. This method is applied for a capacitive discharge containing fluorocarbon, argon and xenon. The electron temperatures and electron densities obtained under various discharge conditions are compared with those reported in the literature by other techniques.