Star-shaped poly(2-methyl-2-oxazoline) (POZO) was prepared by ring-opening polymerization of 2-methyl-2-oxazoline from a novel calix[4]resorcinarene with reactive bromoethyl groups (8Br-CX4) as an initiator. The core-first method, which uses an active multifunctional core to initiate growth of polymer chains, was applied for synthesis of star-shaped POZO based on 8Br-CX4. The obtained star-shaped POZOs were characterized by H-1 NMR, C-13 NMR, FT-IR and DSC. From H-1 NMR, DLS and fluorescence measurements, the star-shaped POZOs formed nanometer scale micelles in aqueous media composed of hydrophobic calix[4]resorcinarene moieties and hydrophilic POW groups.