A novel method for the oxidative trifluoromethylthiolation of cycloalkanols by AgSCF₃/K₂S₂O₈ is described. The methodology provides an efficient and regioselective approach to distally trifluoromethylthiolated ketones in moderate to good yields. The reaction that is easily handled has a good functional-group tolerance and broad scope. Initial mechanistic studies indicate that the reaction may proceed via a radical pathway involving a tandem C(sp³)–C(sp³) bond cleavage and C(sp³)–SCF₃ bond formation process.