An efficient and practical phosphine-catalyzed homo-coupling reaction of benzyl chlorides is described. The reactions proceed smoothly in the presence of CsF/B(OMe)₃ and NaH as the base, respectively, to provide trans-stilbenes in good yields with a broad scope. Unsymmetrical stilbenes are also generated from the reactions of benzyl chlorides with phosphonium salts. Several P-based key intermediates have been detected by NMR and HRMS analyses, which shed light on the postulated catalytic cycle. In the presence of different bases, the transformations involve two different pathways, in which phenylcarbene and phosphonium alkoxide are considered as key intermediates, respectively. The two pathways are complementary in synthesis but different in mechanisms. The synthetic utility, including gram-scale reactions and straightforward access to π-conjugated molecules, has been demonstrated as well.