A soluble well-defined 9,10-diphenylanthryl-bridged ladder polysiloxane (DPAnLP) was prepared via supramolecular assembly-directed condensation polymerization of silanols. The ladder superstructure (LS) was obtained via a synergistic interaction of H-bonding and pi-pi stacking between polymerizable precursor 2-tert-butyl-9,10-bis(methyldihydroxylsilyl)anthracene in organic solvent. The resultant LS was then used as template to direct the condensation of silanol groups to obtain DPAnLP with high regularity. It was found that DPAnLP can emit blue light (430 nm) with great stability and high efficiency in both solution and solid film, which indicated a well organizing of fluorophore within confined environment (ladder structure). TGA and DSC measurements showed that DPAnLP had good thermal stability, and cyclic voltammetry detection gave a low-lying highest occupied molecular orbital level. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2491-2497, 2010