Abstract The radiative recombination efficiency (RRE) of AlGaN quantum wells on epitaxially laterally overgrown AlN/sapphire templates was investigated by picosecond-laser–excited photoluminescence (PL) spectroscopy under selective and non-selective excitation conditions. The PL efficiency, which was deduced by excitation-power-dependent PL measurements at low temperature (LT) and room temperature (RT), was unity at LT under both excitation conditions; However, at RT, the PL efficiency under non-selective excitation conditions was lower than that under selective excitation conditions. Time-resolved PL measurements revealed that, under non-selective excitation conditions, additional carriers are provided from the surrounding layers to the quantum-well layers, especially at LT. Therefore, at RT, the PL efficiency does not correspond to the RRE under non-selective excitation conditions. We propose a model to explain carrier dynamics under the two excitation conditions showing that the PL efficiency equals the RRE under selective excitation conditions.