Communication: A novel 2,5-dipropylhydroquinone-bridged ladder-like polymethylsiloxane (HQBLPS) was successfully synthesized by means of a hydroquinone H-bonding self-assembling template in three main steps, including hydrosilylation coupling, hydrolysis and poly-condensation. It is essential to strictly control the reaction conditions to bring the H-bonding template into full play throughout the whole synthetic process. The factors affecting stereoregularity and molecular weight of the HOBLPS are discussed.