Using time‐resolved photoluminescence, we have examined the optoelectronic properties of Ga0.5In0.5P/GaAs/Ga0.5In0.5P double heterostructures grown by organometallic chemical vapor deposition. For comparison, similar structures using Al0.4Ga0.6As/GaAs and Al0.5In0.5P/GaAs lattice‐matched heterointerfaces were also examined. For the Ga0.5In0.5P/GaAs heterostructure, we show that the recombination velocity at a Ga0.5In0.5P/GaAs interface can be less than 1.5 cm/s. As a result, photoluminescence decay times as long as 14 &mgr;s have been observed in undoped GaAs double heterostructures. This photoluminescence decay time varies with temperature asT1.59, characteristic of radiative recombination not limited by surface or bulk nonradiative recombination processes. For the Al0.4Ga0.6As/GaAs and Al0.5In0.5P/GaAs heterostructures examined in this study, the upper limits of the interface recombination velocity were 210 and 900 cm/s, respectively.