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[Display omitted] • Fire extinguishing experiments of R123 and R125 were performed using the cup burner. • The MEC of R123 is lower than R125. • From the change of flame height and width, the suppression effect of R123 is better than that of R125. • The addition of R123 did not cause a significant temperature change in the flame. • The reaction pathways of thermal decomposition and R123 with H and OH radicals were calculated by DFT. Fire extinguishing performance and mechanism of C 2 HF 3 Cl 2 (R123) were studied by experimental and theoretical methods. The minimum extinguishing concentration (MEC) of R123 in methane/air flames is 7.31 %. The addition of R123 to flame increased first and then decreased the flame height, due to the effect of R123 on the movement of the reaction kernel. Theoretical calculations indicated that R123 and pyrolysis products affect the combustion reaction, the generated fluorine or chlorine-containing groups improved the suppression of combustion chain reactions. The in-depth experimental and theoretical study of R123 boost the development of ideal halon replacement in aircraft cargo compartment. [ABSTRACT FROM AUTHOR]