Highly water soluble [60]fullerene (C-60) end-capped vinyl ether (VE) oligomers with well-defined structure were synthesized by living cationic polymerization technique. The addition reaction between 1-octynylfulleride anion and oligomeric cationic species of VEs with pendant acetoxyl or malonic ester functions afforded the precursor C-60 end-capped oligomers. The living VE oligomers were prepared by living cationic polymerization of diethyl 2-(vinyloxy)ethylmalonate (VOEM) and 2-acetoxy-ethyl vinyl ether (AcOVE) by the CH3CH(OR)Cl/ZnI2 [R = CH2CH2OCOCH3 and CH2CH2CH(COOEt)(2), respectively] initiating system. The precursors were obtained as dark brown gummy solid in 33 and 72% yield for AcOVE and VOEM, respectively. UV-vis and C-13 NMR spectroscopy indicated the formation of 1,2-disubstituted dihydrofullerene derivatives. Hydrolysis of the precursors proceeded quantitatively to give the water-soluble C-60 end-capped oligomers having oligo(sodium 2-vinyloxyethylmalonate) [oligo(VOEMNa)] and oligo(2-hydroxyethyl vinyl ether) [oligo(HOVE)] moieties. Solubility measurements revealed the water-soluble C-60 end-capped oligomer with oligo(VOEMNa) chain to have the excellent aqueous solubility compared to that of the water-soluble C-60 derivatives thus far known; the maximum solubility in water is 96.6 mg/mL, which corresponds to 25.9 mg/mL of the C-60 moiety.