The potential of radiofrequency glow-discharge-optical emission spectrometry (rf-GD-OES) for quantification of thin films on non-conducting materials has been investigated. A commercial rf-GD chamber from Jobin Yvon operated at 13.56 MHz with Ar as discharge gas was used. The signal integration time was 0.1 s. The effect on emission yields of thin conducting layers on glasses of different thickness was studied in detail, using the rf-GD in the common operating mode "constant pressure-constant forward power". Calibration curves were obtained for two types of material-conducting reference materials and a set of non-conductors comprising homogeneous glass of known composition and three different thicknesses coated (or not) with thin layers of gold. Qualitative and quantitative in-depth profile analyses of different coated non-conducting samples were investigated. A variety of samples, including different thick glass substrates (from 1.8 to 5.8 mm), different thin films deposited on homogeneous glasses (from 6 nm to 35 nm), and different kinds of coating (conductors such as Fe, Ni, Cr, Al, and Nb and non-conductors such as Si3N4) were studied at 450 Pa pressure and 20 W forward power. The quantitative in-depth profiles proved satisfactory and results for depths and concentrations were similar to nominal values.