Stellate silver particles, which have from 24 to 56 arms with a length of 30–40 μm, have been synthesized for the first time. The synthesis has been performed by the chemical reduction of an aqueous solution of silver nitrate by a urea alkaline solution under illumination at room temperature. Stellate Ag particles are hydrophobic and have the relative density lower than the density of water. Varying pH and the relation between the concentrations of reagents, one can obtain superhydrophobic powders and films consisting of stellate Ag particles with different lengths of arms.