The development of efficient methods for the cycloaddition of CX 2 (carbon dioxide (X=O) or carbon disulfide (X=S)) with fluorinated epoxides to produce five-membered cyclic carbonates (CCs) or cyclic xanthates (XAs) is a very attractive topic. In this work, the cycloaddition of CX 2 with hexafluoropropene oxide (HFPO) was performed in the presence of a lithium bromide (LiBr) catalyst and optimized in terms of temperature, solvent, pressure, and reaction time. Then, the optimized conditions were tried in the cycloaddition of CX 2 with 2-(trifluoromethyl)oxirane (TFEO) for reproducibility, leading to the corresponding products in high yields. Finally, two original fluorinated five-membered bis-CCs and bis-XAs were synthesized in high yields (85 and 87%) by reacting CX 2 with 1,4-bis(2 ′ ,3 ′epoxypropyl) perfluorobutane (BEPFB). All of the resulting compounds were characterized by FTIR, 1 H, 19 F, and 13 C NMR spectroscopy.