A highly performing and durable forward osmosis (FO) membrane was prepared using a polydopamine-modified polyolefin (DPO) support via an aromatic solvent (toluene)-based interfacial polymerization (IP). The hydrophobic polyolefin support was uniformly hydrophilized by polydopamine coating, which provided long term operation stability. In addition, a highly permselective selective layer was prepared on the hydrophilic DPO support by the toluene-based IP, which promoted amine diffusion and the subsequent IP reaction. As a result, the prepared DPO-supported TFC membrane exhibited significantly high FO performance, which was ~4.9 times higher FO water flux and ~62% lower specific salt flux than those of a commercial FO (HTI-CTA) membrane in FO mode. Furthermore, its excellent mechanical and chemical stability enabled stable operation.