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We report on the effects of combined strain-compensating and strain-mediating layers of various widths on the optical properties of 1.3 μm GaInNAs/GaAs single quantum well structures grown by metalorganic vapor phase epitaxy (MOVPE). While the emission wavelength of GaInNAs/GaAs quantum wells can be redshifted by the adoption of strain-compensated GaNAs layers, the material quality is degraded by the increased stress at the well/barrier interface. This detrimental effect can be cured by inserting a strain-mediating InGaAs layer between them. Contrary to what is expected, however, the emission wavelength is blueshifted by the insertion of the InGaAs layer, which is attributed to the reduced N incorporation due to the improved interface quality. Our results indicate that the optical properties of MOVPE-grown GaInNAs/GaAs quantum wells can be optimized in quantum efficiency and emission wavelength by combination of strain-compensating and strain-mediating layers with suitable characteristics.