Herein, we describe the preparation of lipophilic polyelectrolyte brush (LPB) and its morphology variation induced by immersing in various organic solvents. In particular, the use of 1,2-dichloroethane resulted in twining of large fibers due to the extension of polymer chains, caused by both good compatibility of nonionic moiety and dissociation of ionic moiety. To our best knowledge, this is the first example for PE brush functioning in nonpolar organic media.