Optical properties of the GaNAs/GaAs triple quantum well structures were characterized by using photoreflectance and photoluminescence spectroscopy at different temperatures. The excitonic interband transitions of the triple quantum well systems were observed in the spectral range above hν=Eg(GaNxAs1−x). A matrix transfer algorithm was used to match the GaNxAs1−x/GaAs boundary conditions and calculate the triple quantum well subband energies numerically for theoretical comparison. The internal electric field in the system was extracted from Franz–Keldysh oscillations in the photoreflectance spectra. The influences of the annealing treatment on the transition energy and the internal electric field are also analyzed.