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The degradation of S-nitrosothiols (RSNOs) to release NO is believed to be catalyzed by CuI ions, but the mechanism remains unclear. Kinetic experiments have shown that decomposition rates vary significantly with the chemical nature of the RSNO considered. On the basis of first-principles calculations, the catalytic role of CuI ion is investigated for the decomposition of S-nitrosocysteine and its N-acetylated and ethyl ester derivatives, and for S-nitrosohomocysteine. This preliminary study focuses on the CuI-RSNO intermediates involved in the decomposition pathway. The model chemistry has been validated by comparing calculated CuI-ligand binding energies and S-N bond homolysis energies with available experimental data. Calculations show that the formation of CuI-RSNO intermediates results in weakening of the S-N bond and strengthening of the N-O bond, which would promote S-N bond breaking and NO release from S-nitrosothiols.