SiO2 and SiNx layers are routinely deposited onto III-V(100) surfaces at different device processing steps. We elucidate these insulator-interface properties with photoemission and photoluminescence (PL) of SiO2- and SiNx-capped GaAs(100) surfaces of GaInAsN/GaAs quantum wells (QWs). Post-growth annealing led to an increase of the QW-PL intensity, of which origin can be clearly linked to the SiO2 and SiNx interfaces. Concomitantly, Ga2O–related photoemission increased, indicating useful formation of Ga2O at both insulator interfaces. Furthermore, higher Ga-oxidation-state emission, identified with Ga diffused into SiO2 and SiNx, correlates with the blue-shift of the QW-PL wavelength. Also, interfacial As-As related photoemission was identified.