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In this paper, we present the application of photoreflectance (PR) spectroscopy to investigate the energy level structure of GaInNAs-based quantum wells (QWs). Series of single GaInNAs/GaAs QWs with different nitrogen and indium contents are analysed. The electron effective mass (m e*) and conduction band offset (Q C) are determined and compared with the literature data. The Q C in GaInNAs/GaAs system in the range of investigated GaInNAs content (28–41% of In, 0.3–5.3% of N) has been found to be almost the same as for GaInAs/GaAs system, ie. In addition, the energy level structure for the step-like GaInNAs/Ga (In) NAs/GaAs QWs tailored at 1.3 and 1.55 µm and the Sb-containing Ga (In) NAs/GaAs QWs is investigated. Also, the character of PR transitions, the influence of rapid thermal annealing (RTA) on the energy level structure, and the influence of the carrier localization effect on the efficiency of PR …