This work presents the deep-level photoluminescence of coherently strained GaAsNGaAs quantum-well (QW) structures with various GaAsN thicknesses and N contents. A broad deep-level emission at ∼1.1 eV is observed, whose wavelength is redshifted as the GaAsN thickness increases. Based on its energy separation from the QW emission, this emission is attributed to a transition between the QW electron ground state and a deep level at ∼0.2 eV above the GaAsN valence-band (VB) edge. This level is shown to be tied to the GaAs band edge. A transition between this level and the GaAs conduction band allows the GaAsN-GaAs band alignment to be evaluated. A type II band lineup is obtained with VB offsets of 0.03 and 0.002 eV for N=0.6% and 1.8%, respectively. The decreased VB offset suggests a transition from type II to type I with increasing N content. Thermal annealing effectively removes this level and improves the QW emission. The concentration of this level is not clearly correlated with N content, suggesting that this level is induced by a low-temperature growth of the GaAsN layer to suppress the composition fluctuation. Given its energy, this level is tentatively assigned to VGa.