In this study a series of novel semifluorinated ABA triblock copolymers with different fluorinated segment lengths and different fluorocarbon side-chain structures were synthesized via atom transfer radical polymerization (ATRP) and macroinitiator techniques. The macroinitiator, telechelic bromine terminated polystyrene, was obtained from bulk ATRP of styrene with alpha,alpha'-dibromo-p-xylene as the initiator and cuprous bromide/alpha,alpha'-bispyridine complex as the catalyst. The polymerization reactions of 2-[(perfluorononenyl)oxyl ethyl methacrylate and ethylene glycol monomethacrylate monoperfluorooctanoate were initiated by the macroinitiator in the presence of additional catalyst. The characterization of the block copolymers was performed by gel permeation chromatography, H-1-NMR spectroscopy, and differential scanning calorimetry. The surface activities of the block copolymers in toluene were investigated with the Wilhelmy plate method. The solid surface energy of the block copolymers was determined by measurement of the contact angles.