A novel soluble, reactive ladderlike 4,4'-phenylene ether-bridged polyvinyl-siloxane (L) was synthesized successfully for the first time by a stepwise coupling polymerization (SCP) including hydrolysis and polycondensation. The monomer, 4,4'-bis(vinyldimethoxysilyl )phenylene ether (M), was synthesized by Grignard reaction. The structures of the monomer and the polymer were characterized by infrared spectrometry (IR), nuclear magnetic resonance (H-1 NMR, C-13 NMR, Si-29 NMR), mass spectrometry (MS), differential scanning calorimetry (DSC), X-ray diffration (XRD), and gel permeation chromatography (GPC). It is proposed from the characterization data that the polymer possesses an ordered ladderlike structure.