Effects of rapid thermal annealing and SiO2 encapsulation on GaNAs/GaAs single quantum wells grown by plasma-assisted molecular-beam epitaxy were studied. Photoluminescence measurements on a series of samples with different well widths and N compositions were used to evaluate the effects. The intermixing of GaNAs and GaAs layers was clearly enhanced by the presence of a SiO2-cap layer. However, it was strongly dependent on the N composition. After annealing at 900 °C for 30 s, a blueshift up to 62 meV was observed for the SiO2-capped region of the sample with N composition of 1.5%, whereas only a small blueshift of 26 meV was exhibited for the bare region. For the sample with the N composition of 3.1%, nearly identical photoluminescence peak energy shift for both the SiO2-capped region and the bare region was observed. It is suggested that the enhanced intermixing is mainly dominated by SiO2-capped layer induced defects-assisted diffusion for the sample with smaller N composition, while with increasing N composition, the diffusion assisted by interior defects become predominant. © 2001 American Institute of Physics.