This study reports the synthesis of regioregular poly(3-hexylthiophene)-b-poly(1H,1H-dihydro perfluorooctyl methacrylate) (P3HT-b-PFOMA) block copolymers by atom transfer radical polymerization of FOMA using P3HT macroinitiators. The P3HT macroinitiator was previously prepared by chemical modification of hydroxy terminated P3HT. The block copolymers were characterized by (1)H-NMR, (13)C-NMR, GPC, DSC, TGA and TEM. The block copolymers are able to self-assemble into phase separated micellar thin film morphology from chloroform.