State‐of‐the‐art quality Al0.3Ga0.7As was achieved on both (111)B and (100) GaAs by molecular beam epitaxy. Low‐temperature photoluminescence linewidths of 2.9 and 2.4 meV were obtained for (111)B and (100) Al0.3Ga0.7As, grown at 650 and 700 °C, respectively, with nearly equivalent integrated luminescence intensity. This is the narrowest linewidth ever reported for (111) AlGaAs. The low growth temperature and high material quality of (111)B Al0.3Ga0.7As is expected to be an important factor to the future development of both electronic and optical heterostructure devices.