A thermally stable and solvent resistant conductive polymer composite and its manufacturing friendly preparation method are disclosed. The disclosed composite presents great electrical conductivity with thermal stability and solvent resistance. A method of mixing a host conjugated polymer and a crosslinkable silane precursor simultaneously introduces both dopant and rigid cross-linked siloxane network into polymer system. The thin film made by the disclosed thermally stable and solvent resistant conductive polymer composite can be applied to fabricate various devices.