We describe a facile one-pot process to synthesize Ag nanoplates by reducing silver nitrate with 3,3′,5,5′-tetramethylbenzidine (TMB) at room temperature. The silver nanoplates were highly oriented single crystals with (111) planes as the basal planes. TMB can be readily oxidized to charge-transfer (CT) complex between TMB, as a donor, and (TMB)2+, as an acceptor. The π−π interaction of the neutral amine (TMB) and diiminium structure (dication, TMB2+) result in the formation of one-dimensional CT complex nanofiber. The shape of silver nanostructures and the size of CT complex nanofibers could be controlled by tuning the initial molar ratio of TMB to Ag. This wet-chemical route provides a new concept for simultaneous preparing metal and CT complex nanostructures