The development of efficient methods for the cycloaddition of CX2 (carbon dioxide (X=O) or carbon disulfide (X=S)) with fluorinated epoxides to produce five-membered cyclic carbonates (CCs) or xanthates (XAs) is a very attractive topic. In this work, the cycloaddition of CX2 with hexafluoropropene oxide (HFPO), 2-(trifluoromethyl)oxirane (TFEO), and 1,4-bis(2',3'-epoxypropyl) perfluorobutane (BEPFB) catalyzed by lithium bromide (LiBr) is described. The listed reactions were optimized in terms of temperature, solvent, pressure, and reaction time to lead to a series of original fluorinated five-membered CCs and XAs in high yields (81-93%). The resulting compounds were characterized by FTIR, 1 H, 19 F, and 13 C NMR spectroscopy.