A novel stereo‐regular organo‐bridged ladder‐like polymethylsiloxane ( LPMS ) was synthesized by a stepwise coupling polymerization on the basis of an amido H‐bonding‐assisted self‐assembling template. The monomer N,N′‐bis{4‐3‐(diethoxymethylsilyl)propoxy]‐phenyl}terephthalamide ( M ), prepared by hydrosilylation reaction at high temperature, was hydrolyzed in a dilute solution at a low temperature to form a ladder‐like supramolecular intermediate through amido H‐bonding interactions, which was further condensed to form the polymer LPMS . A combination of techniques including 1H NMR, 29Si NMR, and FT‐IR spectroscopies X‐ray diffraction (XRD), and differential scanning calorimetry (DSC) were used to characterize the titled polymer LPMS , and the results indicate that the polymer possesses an ordered ladder‐like structure.
