We have studied the growth of InGaAs/GaAs multiple quantum wells (MQWs) on (111)A GaAs. Uniform thickness of (111)A quantum wells is observed by the cross‐sectional transmission electron microscopy (TEM). Growth induced long‐range In‐ and Ga‐rich InxGa1−xAs/InyGa1−yAs superlattice in (111)A is also observed by cross‐sectional TEM in the ternary InGaAs wells. In contrast, none of the above superstructure was observed by TEM on a side‐by‐side grown (100) oriented substrate. However, the photoluminescence (PL) linewidth is broadened by such compositional modulation. Low‐temperature (15 K) photoluminescence showed a broad PL linewidth of 27.5 meV for In0.16Ga0.84As/GaAs MQWs grown on (111)A substrates at 520 °C. A decreased PL linewidth of 15.7 meV and a reduced compositional modulation in InGaAs wells can be achieved at a higher growth temperature of 560 °C. ©1996 American Institute of Physics.