A silver-mediated homocoupling of N-triftosylhydrazones for the construction of trans-stilbenes has been presented. This protocol is characterized by its suitability for both inter- and intramolecular reactions, operational simplicity, high efficiency with excellent stereoselectivity, broad substrate scope, and good functional group tolerance. A plausible mechanism involving nucleophilic attack of in situ generated sulfonium ylides on silver carbene was proposed on the basis of experimental results and DFT calculations, which further indicates that π-π stacking interactions play a dominant role in stereoselectivity control.