Abstract: Macro-intermediate with Br-end Poly(tert-butyl methacrylate) (PtBMA-Br) was synthesized by Atom Transfer Radical Polymerization (ATRP)，with ethyl-2-bromopropionate as initiator，a compound system of CuCl/ N,N,N′,N″,N″-penta-methyldiethylenetri-amine (PMDETA) as catalyst. Then hydrophobic macromonomers were synthesized through introducing C=C double bond to the end of poly(tert-butyl methacrylate) by nucleophilic substitution with methacrylic acid. The results of spectral methods (FTIR and 1H-NMR) showed clearly defined structure of macromonomers and high introduction rate of C=C double bond. The molecular weight and polydispersity of the macromonomers were controllable because of the living nature of the atom transfer radical polymerization. Further，polymeric microspheres were prepared by dispersion copolymerization of macromonomers and styrene，with azo-bis-isobutyronitrile (AIBN) as initiator，ethanol as solvent. Scanning electron micrograph (SEM) showed regular shape of copolymeric microsheres.