Abstract: Freon-114 (CClF_2CClF_2) with a pressure of 10 Torr is irradiated by means of a pulsed CO_2 laser at 10.6μm and 9.6μm, each of which corresponds to a specific C—F stretching band of gauche isomer. At both wavelengths, the reaction products are always CF_2Cl_2 and C_2F_4, which result from two different decomposition channels i.e. C—C bond breaking and C—Cl bond breaking. There is thermal effect in the laser induced decomposition of Freon-114, which may be approximately described by an Arrhenius formula. The activation energy E_a of laser induced decomposition for the two different channels canbe estimated from the experimental results. The values of E_a are approximately equal to that obtained from thermal decomposition. At the same time, the channel competition processes of unimolecular laser induced decomposition of Freon-114 can be interpreted by the RRKM theory of unimolecular reaction and the calculated results are in agreement with the experimental results.