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The formation of a weak Cl⋯O bond has been discerned both experimentally and computationally in our studies on the trimethyl phosphate (TMP)–CCl4 system. TMP and CCl4 were codeposited in a nitrogen matrix and adducts of these species were identified using infrared spectroscopy. Formation of the weak adducts were evidenced by shifts in the vibrational frequencies of TMP. The structures and the vibrational frequencies of these adducts were computed at the HF/6-31G** level and the computed vibrational frequencies compared well with the observed frequencies. The nature of the bonding in this adduct was also studied using the atom-in-molecule theory, which clearly showed a (3, −1) bond critical point between the two submolecules. The stabilization energy of these adducts, were computed both at the HF/6-31G**//HF/6-31G** and MP2/6-31G**//HF/6-31G** levels after correcting for zero-point energies and basis set superposition errors. [Copyright &y& Elsevier]