Them onofluoroalkenes ubstructure shows ah igh potentiala saf luorinated synthon in organic synthesis. However, control of the Z/E stereoselectivity of multi-substituted monofluoroalkenep roducts in one-pot reactions still remains ac hallenge. An unprecedented one-pot approach for the highly regio-ands tereoselective preparation of functionalized (Z)-b-monofluoro tri-substituted alkenes from readily available b-chloro-a,b-unsaturated aldehydes or ketones has been explored. Mechanistic studies demonstrated that the reactioni si nitiated by dehy-drochlorination of the substrates to give alkynyl aldehydes/ketones,f ollowed by their trans-hydrofluorination. It is worth mentioning that af luorinating reagent with suitable basicity andn ucleophilicity plays ak ey role in promoting the formationo f( Z)-bfluoro-b-aryl tri-substituted monofluoroalkenes.