Abstract We report on suppression of the Stark effect in (1.5-2)-monolayer(ML)-thick (GaN/AlN)₁₀₀ multiple quantum well (MQW) structures grown on AlN/c-Al₂O₃ templates by plasma-assisted molecular beam epitaxy. Different stress relaxation mechanisms are revealed in these structures by using a multi-beam optical stress sensor in comparison with the 5ML-MQW structure. The former (with well thicknesses ⩽2MLs) demonstrate the nearly stress-free growth, whereas the latter structure with thicker wells exhibits the slow stress evolution from the high initial compressive stress to the nearly relaxed state with zero stress. Moreover, the former structures demonstrate a bright room-temperature cathodoluminescence (CL) with the single peak at the shortest wavelength 240 nm (1.5ML-QWs), while the latter shows much weaker multi-peak CL spectra in the spectral range of 270-360 nm.