Pressure-dependent photoluminescence (PL) in several GaInP(ordered)-GaAs quantum well structures grown by metal organic vapor phase epitaxy is reported. Quantum well emission from GaAs is observed only in structures where thin(∼2 nm)GaP layers are inserted between the GaAs well and the GaInP barrier. By extrapolating the energies of the various inter and intralayer PL transitions observed under pressures (up to 5.5 GPa) to zero pressure, the different band offsets of the heterostructure have been determined. ©1997 American Institute of Physics.