Fluoroalkyl end-capped homo- and cooligomers containing silsesquioxane segments were prepared by the reactions of fluoroalkanoyl peroxides with the corresponding methacrylate monomer-bearing silsesquioxane unit (Si-MMA) and comonomers such as N,N-dimethyl-acrylamide (DMAA) and acrylic acid (ACA). These new fluorinated Si-MMA oligomers were easily soluble in various organic solvents and were able to reduce the surface tension of m-xylene effectively. The modified poly(methyl methacrylate) [PMMA] and glass surface treated with fluorinated Si-MMA homo-oligomers exhibited a strong oleophobicity, although these fluorinated oligomers possess high oleophilic silsesquioxane segments. In contrast, the modified PMMA surface treated with fluorinated Si-MMA-DMAA cooligomers exhibited a good hydrophilicity with a strong oleophobicity. In a series of fluorinated Si-MMA oligomers, fluorinated Si-MMA homo-oligomers had a relatively high thermal stability. Therefore, these fluoroalkyl end-capped Si-MMA oligomers are suggested to have high potential for new functional materials through their unique properties such as a high solubility and surface active properties.