In the presence of Snβ zeolite, vinylarenes undergo the highly chemo- and regioselective head-to-tail heterodimerization with 1,1-diphenylethene to form the corresponding alkenes in good to excellent yields. The scope of the reaction was explored by various vinylarenes with 1,1-diphenylethene. However, the substrates with strong electron-withdrawing groups failed to react with 1,1-diphenylethene under the present catalytic conditions. Moreover, the Snβ zeolite is recyclable and can be reused without significant loss in its catalytic activity.