The novel trans-stereo-regular silylene-thiophene derivatives (4, 5) with perfect consecutive silylene-arylene-silylene-vinylene linkage were synthesized via silylative coupling polycondensation of 2,5-bis(vinyldimethylsilyl)thiophene (2) or 5,5 ' bis(vinyldimethylsilyl)-2,2 '-bithiophene (3) catalyzed by ruthenium-hydride complex [RuHCl(CO)(PCy3)(2)] (1). Their spectroscopic, absorption, and luminescence properties were characterized and compared with those of model compounds containing thiophene or bithiophene chromophores. (c) 2007 Wiley Periodicals, Inc.