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Fluoroform is considered as an ecologically acceptable alternative to chlorofluorocarbons (CFCs). In contrast to CFCs, this compound is stable to near UV light, but it could be decomposed by VUV or ionizing radiation. Basic mechanisms of such processes were revealed in our recent matrix isolation studies [1, 2]. An important feature of these processes is prominent environment effect on the decomposition pathways. It is known that fluoroform yields weak intermolecular complexes with different molecules, including those of interest for atmospheric chemistry. These species are stable, at least, under matrix isolation conditions. The impact of intermolecular interactions on the processes induced by high-energy radiation is poorly studied, and this is an important issue for atmospheric chemistry, astrochemistry and basic chemical physics. In this work we report a FTIR matrix isolation study on the radiolysis at 5 K in the CHF3/CO/Ng systems (Ng = Noble gas). It was shown that codeposition of CHF3/CO/Ng gas mixtures led to formation of CHF3...CO complexes [3]. The spectroscopic characteristics of complexes calculated at the CCSD(T) and MP2 levels of theory are in good agreement with experimental observations. The complexation with CO results in decrease in the yields of all the radiolysis products, except for CF3 radical. This result may be attributed to additional stabilization of CF3 due to formation of CF3...CO complex. The mechanisms of the radiation-induced transformations of different complexes and spectroscopic features of the corresponding radiation-induced intermediates are discussed.