Amphiphilic organic/inorganic hybrid star-shaped polymers (SPP) were prepared by atom transfer radical polymerization (ATRP) using poly(ethylene glycol) methyl ether methacrylate (PEGMA) and 3-(3,5,7,9,11,13,15-heptacyclohexyl-pentacyclo[9.5.1.1³,⁹.1⁵,¹⁵.1⁷,¹³]-octasiloxane-1-yl)propyl methacrylate (MA-POSS) as monomers and octakis(2-bromo-2-methylpropionoxypropyldimethylsiloxy)-octasilsesquioxane (OBPS) as an initiator. Star-shaped polymers (SPM) having PEGMA and methyl methacrylate (MMA) moieties were also prepared for comparative purposes. Polysulfone (PSf) ultrafiltration membranes coated with the SPP showed higher bio- and oil-fouling resistance and flux-recovery ability than the bare PSf membrane. Moreover, the SPP-coated membranes exhibited better antifouling properties than the SPM-coated membrane when they were used for oil/water emulsion filtration. The dual effective antifouling properties of the SPP were ascribed to the simultaneous enrichment of hydrophilic PEG and hydrophobic POSS moieties on the membrane surfaces resulting in the decrease in interactions with proteins and the increase in repellence to oils.