Abstract <p>A plasma-chemical process resulting from a microwave discharge initiated in metal–dielectric powder mixtures was used to produce luminescent materials based on Al₅O₆N doped with Ce³⁺ ions. The self-non-selfsustained discharge was initiated by microwave radiation pulses with a frequency of 75 GHz, power of 400 kW, and duration of 8 ms in Al/γ-Al₂O₃/melamine powder mixtures, cerium was introduced in the form of CeO₂ and Ce(acac)₃·H₂O, and by preliminary doping of γ-Al₂O₃ with Ce³⁺ ions. Kinetic parameters of the plasma-chemical process were determined, microscopic and X-ray diffraction analyses of the products were conducted, and pulsed cathodoluminescence spectra were recorded. It was shown that the rate of the plasma-chemical process and the efficiency of Ce³⁺ ions introduction into the produced Al₅O₆N aluminum oxynitride phase are determined to a large extent by the form of cerium present in the reaction mixture.</p>