AbstractWe present an alternative method for determining the shear deformation potential b of the valence band in III‐V semiconductors. Instead of bulk semiconductors we use quantum well structures and apply uniaxial stress perpendicular to the growth direction. Using analytical solutions we show that the first confined hole state has a pronounced and characteristic nonlinear energy shift with respect to stress. This allows the hydrostatic and shear deformation potentials a and b to be determined independently from the stress dependence of the bandgap only, which can be measured by a wider range of experimental techniques than those necessary for obtaining deformation potentials from bulk material. Measurements on a (GaAs)10/(AIAs)10 superlattice yielded a value for b which is in good agreement with recent results from bulk measurements and hence support the validity of our proposed method.