We report the determination of band offset ratios, using photoluminescence excitation measurements, for GaInP/GaAs and AlInP/GaAs quantum wells grown by gas-source molecular beam epitaxy. To reduce the uncertainty related to the intermixing layer at heterointerfaces, the residual group-V source evacuation time was optimized for abrupt GaInP/GaAs (AlInP/GaAs) interfaces. Based upon thickness and composition values determined by double-crystal x-ray diffraction simulation and cross-sectional transmission electron microscopy, the transition energies of GaInP/GaAs and AlInP/GaAs quantum wells were calculated using a three-band Kane model with varying band-offset ratios. The best fit of measured data to calculated transition energies suggests that the valence-band offset ratio (Γ band discontinuity) was 0.63 ± 0.05 for GaInP/GaAs and 0.54 ± 0.05 for AlInP/GaAs heterostructures. This result showed good agreement with photoluminescence data, indicating that the value is independent of temperature.