New unsymmetrical trans-stilbenes have been prepared by the sequential coupling reactions of bromobenzenesulfonate with formylarylboronic acids, benzylphosphonates and arylmagnesium bromides and characterized. The nickel-catalyzed reactions of stilbenesulfonates with aryl Grignard reagents produced the corresponding stilbenes via the nucleophilic aromatic substitution of the neopentyloxysulfonyl group by aryl nucleophiles. The great chemoselectivity of the alkyloxysulfonyl group allows the stepwise construction of unsymmetrical trans-stilbenes possessing terphenyl moieties. This procedure appears to be a promising and conceptually straightforward route for the parallel synthesis of various unsymmetrical stilbenes as well as other highly conjugated hydrocarbons.