Novel fluorosilicone triblock copolymers poly (2, 2, 3, 4, 4, 4-hexafluorobutyl methacrylate)-block-poly(dimethylsiloxane)-block-poly (2, 2, 3, 4, 4, 4-hexafluorobutyl methacrylate) (PHFBMA-b-PDMS-b-PHFBMA) were synthesized by atom transfer radical polymerization (ATRP). The optimum reaction conditions were also studied in the work. The structure and composition of the copolymers were analyzed and identified by infrared spectroscopy (IR), nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC). The effects of the fluorine and silicone content on the hydrophobic and oleophobic properties of prepared triblock copolymers were also investigated. The results showed that the prepared triblock copolymers had excellent hydrophobic and oleophobic properties.