Low surface energy materials have been extensively investigated for building icephobic surfaces in recent years. Polydimethylsiloxane (PDMS) and fluoropolymers have been introduced to this field, while control of their structures is of importance to produce deicing surfaces. In this work, fluorinated methacrylate block copolymers containing polyhedral oligomeric silsesquioxane (POSS) moieties were synthesized by reversible addition-fragmentation chain transfer polymerization and transformed into thiolated-copolymers by aminolysis to adjust the self-assembly and modify surface morphology. The icephobic coatings were developed via UV-curable thiol-ene reaction with tunable amounts of thiol-modified POSS-fluorinated methacrylate diblock copolymers with vinyl-functionalized PDMS and thiol-functionalized PDMS. Characterizations of atomic force microscopy, X-ray photoelectron spectroscopy, and contact angle showed the evidence of the POSS-fluorinated diblock copolymers on the outmost surface of the coatings. Owing to the crystallization of perfluoroalkyl side groups, the coatings containing thiol-modified poly(methacrylisobutyl POSS)-b-poly(2-perfluorooctylethyl methacrylate) (S17F) exhibited excellent icephobicity, and water droplets could rebound completely on all S17F-containing surfaces at both normal and tilt modes before freeze even at −15 °C. The ice shear strengths of the prepared UV-cured coatings were about one-eighth of that on bare aluminum surface, while the coating containing 5% S17F achieved the lowest ice shear strength of 105 ± 12 kPa. It was found that the icephobicity of these coatings were attributed primarily to the synergistic effect of the POSS-fluorinated methacrylate diblock copolymer and the PDMS component.