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The reaction O( 1 D) + CF 3 Br has been investigated in solid Ar-matrices at T = 14 K. Codeposition of O 3 /CF 3 Br/Ar mixtures and irradiation at 250 nm yielded F 2 CO as dominant reaction product. Experiments with 18 O 3 indicate that CF 3 OBr was formed during the course of the reaction. Our observations were interpreted with the formation of an excited CF 3 OBr molecule which can be stabilized in the matrix cage or decompose rapidly into two different F 2 CO HF complexes.