It has been found that AlAs, AlGaAs, and AlInAs layers grown on 2° misoriented (111)BGaAs substrates by molecular beam epitaxy are much smoother than corresponding (111)GaAs layers. The quality of Al containing (111)Blayers is further demonstrated by the narrow (65 A˚) photoluminescence peak from an AlAs/Al0.5In0.5As strained multiquantum well structure. The photoluminescence spectra of this structure is considered in detail, with particular attention paid to Stark effects associated with strain‐generated internal electric fields. Spectral movement of the photoluminescence peak as a function of excitation intensity suggests the attainment of self‐biased strained quantum wells.