The CF,Br radical is generated by 248 nm laser-flash photolysis of CF, Br,. Its reaction with oxygen is investigated by kinetic spectrophotometry and BrO is observed as an intermediate. To explain this observation, reactions CF2Br + O-2 --> CF2BrO2 and CF2BrO2 + Br --> BrO + CF2BrO are proposed and their rate constants are estimated as (1.6 +/- 0.5) x 10(-12) and (2.4 +/- 0.9) X 10(-11) molecule(-1) cm(3) s(-1), respectively, at 299 +/- 1 K.