2,5-Dihydroxyboryl-1,1-dimethyl-3,4-bis(3-fluorophenyl)-silole (2a) was prepared in 40% overall yield by reaction between 3-fluorophenyl-acetylene and dichlorodimethylsilane to yield bis[2(3-fluorophenyl)ethynyl]dimethylsilane (1a), which subsequently undergoes a reductive cyclization reaction using an excess of lithium naphthalenide. The fluoro substituted silole was applied as a co-monomer in the Suzuki polycondensation reaction with 2,7-dibromo-9,9-dioctyl-fluorene. An oligomer (3a) with a degree of polymerization of 6 was prepared and compared with an oligomer without fluoro substitution on the silole (3b), with a degree of polymerization of 4. The new oligomers were spin coated onto glass slides and showed weak green photoluminescence (PL) in the solid state. Cyclic voltammetry, visible absorption spectroscopy, and density functional theory calculations showed that the fluoro substituents were sufficiently electron withdrawing to lower both the highest occupied molecular orbital and the lowest unoccupied molecular orbital in the oligomer. Two further alternating co-oligomers were prepared from 2,5-dihydroxyboryl-1,1-dimethyl-3,4-bis(phenyl)-silole (2b) and 1,3-dibromo-5-fluoro-benzene (4a) or 1,3-dibromobenzene (4b). These oligomers both had degrees of polymerization of 8 and showed green PL in the solid state. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47:5116-5125, 2009