A novel, soluble terephthalamide-bridged ladderlike polysiloxane (L) was synthesized successfully for the first time by stepwise coupling polymerization. The process involved the hydrogen-bonding self-assembly of amido groups, which resulted in the formation of a more highly ordered polymeric structure. A novel monomer, bis(3-methyldimetlioxysilylpropyl) terephthalamide (M), was prepared by a hydrosilylation reaction in the presence of dicyclopentadienyl platinum dichloride as a catalyst. The structures of the monomer (M) and the polymer (L) were characterized by Fourier transform infrared, H-1 NMR, C-13 NMR, Si-29 NMR, mass spectrometry, X-ray diffraction, differential scanning calorimetry, and vapor pressure osmometry. All the characterization data indicated that the synthesized polymer (L) possessed an ordered ladderlike structure.