The photoluminescence characteristics of pseudomorphic In0.19Ga0.81As/GaAs quantum well structures grown on both the conventional (001) and the unconventional (112)B GaAs substrate are investigated. It is found that the emission spectra of the structures grown on the (112)B surface exhibit some spectral characteristics not observed on similar structures grown on the (001) surface. A spectral blue shift of thee→hh1 transition with increasing optical pump intensity is observed for the quantum wells on the (112) surface. This shift is interpreted to be evidence of a strain‐induced piezoelectric field. A second spectral feature located within the band gap of the In0.19Ga0.81As layer is also observed for the (112) structure; this feature is thought to be an impurity‐related emission. The expected transition energies of the quantum well structures are calculated using the effective mass theory based on the 4×4 Luttinger valence band Hamiltonian, and a related strain Hamiltonian. ©1995 American Institute of Physics.