We deposited an AlGaAs/GaAs quantum well (QW) structure by MOCVD on [011]-aligned pyramids on (100) semi-insulating GaAs substrate. The pyramids were either flat-top or blade-sharp. They were confined at the sides by facets A and B were tilted to (100) at ∼30° and ∼45°, respectively. The AlGaAs/GaAs QW structure overgrew the pyramids continuously. Facets A were fast-growing and facets B were slow growing. The TEM cross-sectional observation showed the GaAs QW layer on facets B was ∼10nm thick. AFM analysis showed that overgrown facets A were rougher than facets B (RMS ∼20nm). A photoluminescence signal corresponding to e1–hh1 transition in QW, with full width at half maximum of 17.6meV, was detected.