Highly efficient synthesis of silyl-substituted oligoarenes with defined structures is achieved by an iterative cross-coupling reaction and deprotection sequence using organo[(2-hydroxymethyl)phenyl]dimethylsilanes. The excellent stability of the tetraorganosilicon compounds as well as mild and divergent conditions for cross-coupling and deprotection steps allows preparation of highly conjugated oligoarenylsilanes such as unsymmetrically disilylated quinquethiophenes.