Self-assembly of bismuth droplets at nanoscale on GaAs(100) surface using molecular beam epitaxy was demonstrated. Fine control of density and size was achieved by varying growth temperature and total bismuth deposition. Droplet density was tuned by roughly 3 orders of magnitude, and the density-temperature dependence was found to be consistent with classical nucleation theory. These results may extend the flexibility of droplet epitaxy by serving as templates for group V based droplet epitaxy, which is in contrast to conventional group III based droplet epitaxy and may encourage nanostructure formation of bismuth-containing materials.