Colloidal “silver stars” were synthesized upon poly(lactic-co-glycolic) acid nanosphere templates via a facile two-step silver reduction method. Myriad dendrimer-like Ag star morphologies were synthesized by varying the amount of poly(vinyl alcohol) and trisodium citrate used during silver reduction. Scanning electron microscopy studies revealed that star-shaped silver–polymer composites possessing nanoscopic, fractal morphologies with diameters ranging from 500 nm to 7 μm were produced. These composites have broad applications from antibacterial agents to catalysis; two such applications were tested here. Surface-enhanced Raman spectroscopy (SERS) studies showed multiple hot spots of SERS activity within a single star. Electrochemical catalysis experiments demonstrated the feasibility of using the silver stars instead of platinum for the oxygen reduction reaction in alkaline fuel cells.