We report star polyhedral gold nanocrystals synthesized by colloidal reduction with ascorbic acid in water at ambient conditions. We identify two distinct classes of star nanocrystals: multiple-twinned crystals with fivefold symmetry, and monocrystals. These respective classes correspond to icosahedra and cuboctahedra, two Archimedian solids, with preferential growth of their {111} surfaces. Due to this preferential growth, the {111} faces of the original Archimedean solids grow to become tetrahedral pyramids, the base of each pyramid being the original polyhedral face. By assuming a star morphology, gold nanocrystals increase their proportion of exposed {111} surfaces, which possess the lowest surface energy among low-index crystallographic planes for FCC crystals. Thus, we propose that the driving force for star nanocrystal formation Could be the reduction in surface energy that the crystals experience. Interestingly, icosahedrally derived star nanocrystals possess a geometric morphology closely resembling the great stellated dodecahedron, a Kepler-Poinsot solid. (c) 2005 Elsevier B.V. All rights reserved.