Silole-core dendrimers having benzyl ether-type dendron units, readily synthesized by the Ni-catalyzed reaction of benzyloxy-substituted diphenylacetylenes with 1, 1, 2, 2- tetramethyldisilane, display, upon excitation of the dendron units, efficient energy transfer from the dendron units to the silole core, resulting in strong emission from the silole ring.