The assembling and self-association of anionic [Au(CN)(2)](-) spatially along cationic beta-sheeted poly-L-lysine, P(Lys), through electrostatic interaction was demonstrated to form luminescent [Au(CN)(2)](-) aggregates, wherein negatively charged [Au(CN)(2)](-) was found to stabilize the beta-sheet structure by suppressing repulsion between the positively charged side chains.