Efficient synthesis of CF3‐functionalized 1,3‐dioxolane phosphonates via base‐catalyzed nucleophilic addition/cyclization of diethyl ethynylphosphonate or diethyl 3‐hydroxyprop‐1‐yn‐1‐ylphosphonates with trifluoromethylketones is described. Synthesis of various CF3‐substituted 1,3‐dioxolane derivatives in good to excellent yields with a broad range of substrates is described.