Cyclization of CO2 (or CS2) coupled with trifluoromethylation was carried out taking allylamine as substrate, Togni's reagent Ⅱ(1-(trifluoromethyl)-1,2-benziodoxol-3(1H)-one) as source of trifluoromethyl, single-site copper of highly stable metal-organic framework (MOF) HKUST-1〔based upon the Cu2(O2C)4 bis-paddelwheel, the simplest molecular structure of catalyst is Cu2(BTC)4/3·2H2O, and the relative molecular weight is about 439.28 g/mol〕as catalyst. The factors affecting the reaction such as basic additive, solvent, reaction temperature, loading amount of HKUST-1 were optimized. The results showed that allylamine substrates bearing different substituent groups could been transformed into bioactive trifluoromethylated 2-oxazolidones in yields of 69%~87% under the optimal conditions of 5% HKUST-1, CO2 pressure 101.325 kPa , reaction temperature 45 ℃. The possible mechanism of the reaction was verified by free radical trapping experiment. The catalyst HKUST-1 could be easily recovered and reused for at least five times and still had good catalytic activity and crystal structure. When CS2 was used as C1 source instead of CO2, the analogue of central nervous system agent, trifluoromethylated 2-thiazolidinethione could be obtained, reflecting the durability of this heterogeneous catalytic system against sulfur-poisoning effect.