We report herein the use of Medicago sativa alfalfa shoot biomass for the removal of gold from aqueous solutions. The accumulation process involves the reduction of Au(Ill) to colloidal Au(O) and is shown to increase at elevated temperatures and at lower pH. X-ray absorption spectroscopy (XAS) was used to determine that gold(Ill) was reduced to form gold(0) colloids, which varied in size depending on the pH of the initial solution. The gold cluster radius was 6.2±1 angstroms at pH 5 and 9.0±1 angstroms at pH 2. Our findings indicate that essentially another layer of gold atoms was deposited onto the colloid surface at pH 2. Possible mechanisms of bioreduction and accumulation are discussed.