Synthetic methods for the preparation of thioketals featuring CF₃ groups are rare. Here, we have developed a copper-catalyzed thioketalization of enones bearing CF₃ groups and various mercaptans. 24 thioketal molecules have been obtained with moderate to excellent yield. Meanwhile, a preparative scale experiment has been performed giving over 95% yield. This work allows the straightforward formation of thioketals containing CF₃ groups and unsaturated double bonds.