Herein, we report the rhodium-catalyzed Z-alkenyl transfer from tertiary allylic alcohols to aryl trifluoromethyl ketones, which provided an efficient way of preparation of trifluoromethyl-containing Z-allylic alcohols via β-Z-alkenyl elimination. The key Z-alkenyl-rhodium species were generated with a high degree of stereochemical retention. This reaction featured a broad substrate scope and good functional tolerance and would offer a fascinating approach for the synthesis of Z-alkenes.