Growing demands for reducing energy consumption have raised interest to design advanced materials for thin film composite (TFC) desalination membranes with high permselectivity and low fouling. Here, we synthesized a star-shaped polymer as a new building block material, which can be assembled into selective layer of the TFC membrane via a facile interfacial polymerization (IP). Star polymer with compact globular structure and high density amine functional groups enabled to fabricate higher permselectivity and lower fouling propensity membrane compared to commercial membranes. In addition, star polymer assembled TFC membrane can function as either nanofiltration or reverse osmosis membrane by simply adjusting IP process conditions, which cannot feasible in conventional materials, demonstrating remarkable versatility of our star polymer.