A novel resin, poly(dimethylsilylene-ethynylene-phenoxyphenoxyphenylene-ethynylene), was synthesized from 1,4-bis(p-ethynylphenoxy)benzene and dimethyldichlorosilane through Grignard reaction. The structures of the monomer and the resin were characterized by elemental analysis, Fourier transform infrared, proton nuclear magnetic resonance, electron ionization-mass spectrometry and gel permeation chromatography. The thermal behaviour of the resin was examined by differential scanning calorimetry. The cured resin exhibits excellent dielectric property, high glass transition temperature, good mechanical properties and high thermal stability. The flexural strength and impact strength of the cured resin were 55.0 MPa and 10.5 KJ m−2, respectively. The degradation temperature at 5% weight loss of the cured resin arrived at 549°C in nitrogen.