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This paper presents a study of the structural and optical properties of strained GaInAs/ InP multiple quantum well (MQW) structures fabricated by LP-MOVPE. The composition of the Ga x In1−x As films ranged fromx = 0.17 tox = 1.0 and was determined by sputtered neutral mass spectrometry (SNMS) on thick layers. The structures of the MQW samples with well widths from 1.5 to 5 nm were investigated by high resolution x-ray diffraction (HR-XRD). Simulations of the diffraction patterns showed that transition layers of approximately 2 monolayer (ML) thickness with high lattice mismatch exist at the interfaces. Photoluminescence (PL) measurements indicate well widths of a multiple of a monolayer with local variations of one monolayer. The PL peak energies vary smoothly with the Ga concentration. These results were confirmed by optical absorption measurements.