A ruthenium-catalyzed oxidant-free highly regioselective ortho alkenylation of substituted aromatics such as aromatic amides, aromatic ketoximes, and anilides with alkenes in the presence of AgSbF6 and acetic acid in ClCH2CH2Cl at room temperature is described. The alkenylation reaction provides ortho alkenylated aromatics along with evolution of H2 gas. In the reaction, no oxidant was used, and the whole catalytic reaction has occurred without changing the oxidation state of the metal. © 2015 American Chemical Society.