Fluoroalkyl end-capped copolymers containing glucosyl segments were prepared by the copolymerizations of fluoroalkanoyl peroxides with 2-glucosyoxyethyl methacrylate (GEMA) and comonomers such as acrylic acid (ACA) and methaerylate monomer-containing poly(oxyethylene) units (PME). Under the non-cross-linked conditions, fluoroalkyl end-capped GEMA-ACA and GEMA-PME copolymers were found to cause a gelation in dimethyl sulfoxide (DMSO), where the aggregations of end-capped fluoroalkyl segments and the hydrogen-bonding interaction between hydroxyl segments are involved in establishing a physical gel network, although the corresponding nonfluorinated GEMA copolymers could cause no gelation in DMSO. More interestingly, it was demonstrated that these fluorinated polymeric gelling electrolytes containing lithium salts exhibit a considerably high ionic conductivity of 10(-3) S/cm level at room temperature.