We report a ring-opening trifluoromethylthiolation of cyclopropanols with TsSCF3 by using Cu(OAc)2 as the catalyst. Moreover, by using this strategy, the trifluoromethylselenolation of cyclopropanols with Se-(trifluoromethyl) 4-methoxybenzenesulfonoselenoate to access β-SeCF3-substituted carbonyl compounds is achieved for the first time. The broad substrate scope, readily accessible reagents and cheap catalyst make this protocol an alternative and efficient method for the synthesis of β-SCF3-substituted or β-SeCF3-substituted carbonyl compounds.