Hydrogenated amorphous silicon–carbon (a‐SiC : H) nanometric powder was produced in an rf plasma of SiH4 and CH4. Particle size, composition and powder yield were controlled by plasma modulation, SiH4/CH4 flow ratio and pressure of the gas mixture inside the plasma reactor. Quasi‐monodisperse silicon–carbon nanopowder, with a size of about 30 nm, was studied by infrared phase modulated ellipsometry (IRPME), scanning (SEM) and transmission (TEM) electron microscopy. The optical properties of the discontinuous powder layer deposited onto non‐insulating substrates were fitted to a three‐layer system. The use of non‐metallic substrates allowed us to identify the contributions of different vibrational groups to the Si–H stretching band. The structural parameters determined by ellipsometry agree with the size, morphology and substrate coverage of the nanoparticles measured by SEM and TEM.