Low concentrations of carbon monoxide (CO) can play vital roles in pharmacological and physiological functions in the human body. The transition-metal carbonyl complexes of the tricarbonyldichlororuthenium(II) dimer [Ru2(CO)6Cl4 (CORM-2)] were proposed as CO-releasing molecules (CORMs) to improve the delivery efficiency of CO for therapeutic effects. The accurate identification of final products for CORMs in solution and the detailed mechanisms of the release of CO were the essential prerequisite for its effective physiological application, which have been deficient. In this study, utilizing the cutting-edge two-dimensional (2D) IR spectroscopy, with the intrinsic vibrational modes and the coupling information on dynamics of intramolecular vibrational energy redistribution (IVR), the final products of A, B, C, and E are accurately identified when CORM-2 is dissolved in dimethyl sulfoxide (DMSO). Furthermore, with the clues on intermolecular interaction and chemical exchange dynamics between different products, the transformations between different products are also directly characterized for the first time. These findings challenge the results from the classic 1D spectroscopic pattern, and they evidently demonstrated that the release of CO from CORM-2 in DMSO was slow and complicated with multiple reaction pathways. Combining with DFT simulations, the detailed mechanisms of release of CO for CORM-2 dissolved in DMSO are schematically proposed, which can significantly contribute to its drug optimization and pharmacological as well as physiological applications.