The highly performing polyamide (PA) thin film composite (TFC) reverse osmosis (RO) membrane was prepared using the commercialized porous polyolefin (PO) membrane as a support. The PO-supported TFC (PO-TFC) membrane was fabricated via a conventional interfacial polymerization process. The highly permselective PA layer was formed by optimizing membrane fabrication parameters such as monomer/additive composition and post-treatment. The uniform pore structure and high surface porosity of the PO support are beneficial for improving the membrane permselectivity. As a result, the prepared PO-TFC membrane showed ~30% higher water flux and ~0.4% higher NaCl rejection compared to a commercial RO membrane. In addition, the PO-TFC membrane exhibited excellent mechanical properties and organic solvent resistance.