Density functional theory methods have been used to investigate the role and effects of Cu+ binding to the S and N centers of the -SNO functional group within S-nitrosothiols (RSNOs), on the lability of the NO group. The binding of Cu+ to the S center is found to weaken the S-N bond, while the N-O bond is concomitantly strengthened, consistent with the notion that Cu+ binding catalyzes NO radical release. In contrast, however, the binding of Cu+ to the N center is found to dramatically shorten and strengthen the S-N bond with a concomitant lengthening of the N-O bond, suggesting stabilization of the RSNOs against NO release. Upon solvation, complexes with Cu+ bound to the N center are stabilized relative to the corresponding S-bound complexes, though remaining slightly higher in energy. The barriers to interconversion between corresponding isomers were also investigated. Implications for biochemical regulation of NO release from RSNOs are discussed.