Dilute nitrides lattice-matched to GaP were studied to explore the possibilities to improve their properties by additional indium or arsenic content in the GaPN alloy for further utilization in solar cells. Admittance spectroscopy shows that intrinsic layers of GaPNAs and InP/GaPN grown by molecular-beam epitaxy have unintentional background silicon donor doping. Deep-level transient spectroscopy allowed us to reveal several defect levels. In GaPNAs, two defect levels were detected at Ec − 0.58 eV and Ev + 0.44 eV, with respective concentrations of 4 × 1015 cm−3 and 2 × 1015 cm−3. After thermal annealing, these could be reduced by a factor of two and by more than one order of magnitude, respectively, leading to an increase of external quantum efficiency and open-circuit voltage of solar cells. The InP/GaPN layer exhibits a defect level at Ec − 0.44 eV (with a concentration of 2 × 1014 cm−3), which is of similar nature as the one at Ec − 0.58 eV in GaPNAs. Furthermore, unlike in GaPNAs, defect levels close to midgap were also detected in the InP/GaPN layer. These non-radiative recombination centers lead to poorer photoelectric properties of solar cells based on InP/GaPN as compared to those based on GaPNAs. Therefore, the introduction of arsenic in the compound and post-growth thermal annealing allowed us to reduce the defect concentrations in dilute nitrides and improve photoelectrical properties for photovoltaic applications.