A novel synthesis method of 1,1-dichlorooctafluorocyclopentane and 1,2-dichlorooctafluorocyclopentane through the reaction of 1,2-dichlorohexafluorocyclopentene, anhydrous hydrogen fluoride (AHF) and chlorine were reported. The new catalyst ZFZCC containing Fe(+3), Zr(+4), Co(+2), Zn(+2) and Cu(+2) were prepared and the mechanism was discussed. Display omitted •A novel method of preparing dichlorooctafluorocyclopentane was reported.•A series of single- and multi-component catalysts was prepared by improving components and methods.•The co-precipitated catalyst containing Fe(+3), Zr(+4), Co(+2), Zn(+2) and Cu(+2) showed the highest catalytic activity.•The catalytic reaction mechanism was put forward. A novel method was used for preparing 1,1-dichlorooctafluorocyclopentane and 1,2-dichlorooctafluorocyclopentane through the reaction of 1,2-dichlorohexafluorocyclopentene, anhydrous hydrogen fluoride, and chlorine. A series of single- and multi-component catalysts were prepared by means of impregnation and coprecipitation, respectively. The catalyst containing Fe(III), Zr(IV), Co(II), Zn(II) and Cu(II) showed the highest catalytic activity among these catalysts. Moreover, the main reaction routes and catalytic mechanism were investigated through experiments and theoretical analysis. Given the environmental and economic benefits, this method has a great application potential in industrial production.