Radical homopolymerization of 2,2,2-Trifluoroethyl acrylate (ATRIF) and their copolymerizations with acrylonitrile (AN) were investigated. The compositions of the resulting copolymers poly(AN-co-ATRIF) were assessed by 1HNMR. The glass transition temperature values Tg of these copolymers increased from 17 to 61 °C as the molar percent of ATRIF deceased in the copolymer. This may arise from the CF3 group of ATRIF which could have a plasticizing effect in the copolymers. The TGA thermgram of poly(ATRIF) hompolymer, recorded under nitrogen, presents one step that occured at onset temperature decomposition around 335 °C, the weight loss at 550 °C close to zero indicating that the thermal degradation of poly(ATRIF) hompolymer is mainly a depolymerization reaction. The TGA thermograms of poly(AN-co-ATRIF) copolymers displays the evolution of the their thermostability with the molar composition. The TGA curves present two steps of thermal degradation of these copolymers. The Thermal kinetic studies of the random copolymers based on acrylonitrile (AN) with 2,2,2-trifluoroethyl acrylate (ATRIF) prepared from an equimolar mixture and of the homopolymer poly(ATRIF) were performed under nitrogen by using thermogravimetric analysis coupled to CG-MS spectroscopy.Various degradation models including the Kissenger–Akahira–Sunose, Friedman, Flynn-Wall- Ozawa, and isothermal methods were used to determine the apparent activation energy of these polymers. The determination of mechanism of degradation for the poly(AN-co-ATRIF) copolymer was performed by using GC-MS to identify the volatile fragments resulting from the first stage of thermal degradation of the copolymer which was heated in the pyrolyser unit at 320 °C. The results obtained by dynamic methods (Friedman and Flynn-Wall-Ozawa and Kissinger) are in good agreement with those obtained by isothermal method. The activation energies for the copolymer are within the range of 204-281 KJ/mol for the first stage of decomposition