Quantum dot (QD) growth on high () symmetry GaAs {111} surfaces holds promise for efficient entangled photon sources. Unfortunately, homoepitaxy on GaAs {111} surfaces suffers from surface roughness/defects and InAs deposition does not natively support Stranski–Krastanov QD growth. Surfactants have been identified as effective tools to alter the epitaxial growth process of III-V materials, however, their use remains unexplored on GaAs {111}. Here, we investigate Bi as a surfactant in III-As molecular beam epitaxy on GaAs (111) A substrates, demonstrating that Bi can eliminate surface defects/hillocks in GaAs and (Al, Ga) As layers, yielding atomically-smooth hillock-free surfaces with RMS roughness values as low as 0.13 nm. Increasing Bi fluxes are found to result in smoother surfaces and Bi is observed to increase adatom diffusion. The Bi surfactant is also shown to trigger a morphological transition in InAs/GaAs (111) A films, directing the 2D InAs layer to rearrange into 3D nanostructures, which are promising candidates for high-symmetry QDs. The desorption activation energy () of Bi on GaAs (111) A was measured by reflection high energy electron diffraction, yielding = 1.7±0.4 eV. These results illustrate the potential of Bi surfactants on GaAs (111) A and will help pave the way for GaAs (111) A as a platform for technological applications including quantum photonics.