High quality GaInAsSb/AlGaAsSb quantum wells (QWs) have been grown by molecular beam epitaxy using proper interface treatments. By controlling the group-V elements at interfaces, we obtained excellent optical quality QWs, which were free from undesired localized trap states, which may otherwise severely affect the exciton recombination. Strong and highly efficient exciton emissions up to room temperature with a wavelength of 2.2 μm were observed. A comprehensive investigation on the QW quality was carried out using temperature dependent and power dependent photoluminescence (PL) measurements. The PL emission intensity remains nearly constant at low temperatures and is free from the PL quenching from the defect induced localized states. The temperature dependent emission energy had a bulk-like behavior, indicating high quality well/barrier interfaces. Because of the uniformity of the QWs and smooth interfaces, the low temperature limit of inhomogeneous line width broadening is as small as 5 meV.