The cationic rhodium(I) complex [Rh(cod)2]BF4 (cod = 1,5-cyclooctadiene) catalyzes the [2 + 2 + 1] cross-cyclotrimerization of silylacetylenes and two alkynyl esters, leading to substituted silylfulvenes. The reductive complexation of the silylfulvene product with RhCl3 in EtOH furnished the corresponding dinuclear electron-deficient cyclopentadienyl rhodium(III) complex. This Rh(III) complex is a highly active and selective precatalyst for the oxidative coupling of acetanilides and alkynes. [on SciFinder(R)]