Rhodium-catalyzed reactions of 3-ethynyl-2-pentamethyldisilanylthiophene derivatives (1a–1c) have been reported. At 110 °C, compounds 1a–1c reacted in the presence of a rhodium complex catalyst, yielding thiophene-fused siloles (2a–2c) through intramolecular trans-bis-silylation. To understand the production of 2a from 1a, the mechanism was investigated using density functional theory (DFT) calculations.