Structural and optical properties of MOVPE-grown GaInNAs quantum wells (QW) with multiple barriers (InGaAs/GaNAs) have been investigated. Significant improvement of optical performance in the 1.3 μm range is demonstrated with the proposed structure. PLE studies show that the density of N-related localized states can be reduced by the introduction of a thin InGaAs layer due to the improved interface quality. Based on the structural analysis, it is concluded that the InGaAs layer supports the nitrogen redistribution within the QW, resulting in a sharp interface. The blue-shift trend of the GaInNAs QW as a function of the GaNAs thickness can be explained by the reduction of the N content in the GaInNAs QW.