Several polyfluoroalkylated heterocyclic compounds containing methylenedioxy group such as 2‐(F‐alkyl) substituted 1,3‐benzodioxole, piperonal, 4H‐1,3‐benzodioxin, 1,3‐dioxolane and 6‐(F‐alkyl) substituted dibenzo[d, f][1,3]dioxepin have been prepared through double Michael‐addition reactions of 2,2‐dihydropolyfluoroalkanoates with the corresponding diphenols or diols in high yields.