Bis(perfluorocyclohexane carbonyl) peroxide was prepared by the reaction of the corresponding acyl fluoride and hydrogen peroxide. This peroxide was applied to the preparation of perfluorocyclohexylated end-capped oligomers via a radical process under very mild conditions. In cyclic perfluorocyclohexylated end-capped oligomers containing hydroxy segments, these oligomers could cause a gelation in water and in polar organic solvents such as MeOH, EtOH, dimethylformamide (DMF), and dimethylsulfoxide (DMSO), and the gelling ability of these oligomers was superior to that of the corresponding linear perfluorooxaalkylated oligomers. Furthermore, perfluroocyclohexylation of polystyrene or benzene was proceeded via a single electron transfer reaction by using this peroxide.