We describe a general procedure for the synthesis of miktoarm star triblock copolymers with a hydrocarbon, a fluoropolymer, and a hydrophilic segment. Several μ-(polyethylethylene)(poly-(ethylene oxide))(poly(perfluoropropylene oxide)) [μ-(PEE)(PEO)(PFPO)] star triblock copolymers were prepared using two successive anionic polymerization steps and one polymer-polymer coupling reaction. Initially, living polybutadienyllithium chains were end-capped with 2-methoxymethoxymethyloxirane forming a heterobifunctional 1,2-polybutadiene (PBD) precursor, with a hydroxyl group and a protected hydroxyl group at one chain end. Catalytic hydrogenation of this PBD gave the corresponding polyethylethyene (PEE) while preserving the end group structures. Transformation of the terminal hydroxyl group in the PEE precursor to a potassium alkoxide followed by addition of ethylene oxide and subsequent end-capping with ethyl bromide generated polyethylethylene-poly(ethylene oxide) (PEE-PEO) diblock copolymers with a protected hydroxyl group at the junction. Deprotection of the methoxymethyl group followed by coupling with acid chloride end-capped PFPO yielded well-defined μ-(PEE)(PEO)(PFPO) star triblock copolymers. Detailed molecular characterization of these products and their precursors confirmed the composition and architecture of these new star block copolymers. This modular strategy represents a new, straightforward, and versatile methodology for the preparation of mixed arm star block copolymers.