Fluoroalkylated oligomers with carbon-carbon bond formation were obtained by reactions of acrylic acid, methyl methacrylate, and ethylene oxide units-containing methacrylates, acrylates with fluoroalkanoyl peroxides in excellent to moderate yields under very mild conditions. A mechanistic study of these reactions was carried out by the MNDO-PM 3 semiempirical MO method. A strong interaction between HOMO of the monomer and SOMO of fluoroalkyl radical produced by the thermal decomposition of the peroxide appeared to cause the addition of the fluoroalkyl radical, to the monomer to afford the corresponding fluoroalkylated oligomer. Fluoroalkylated acrylic acid oligomers were found capable of reducing the surface tension of water to 10 mN/m. Fluoroalkylated-methacrylates, and-acrylates oligomers containing ethylene oxide units became typical fluorinated amphipathic compounds.