Ab initio MO calculations have been performed for the [(CO2)(n)ROH](-) (R=H and CH3) anions with n=1 and 2. Three stable structures are found for [(CO2)H2O](-), and two structures for [(CO2)CH3OH](-). All the [(CO2)ROH](-) structures are characterized by the charge localization on the CO2 moiety, which interacts with ROH through an O-H ... O linkage. It is also revealed that the addition of ROH to CO2-leads to the formation of a potential barrier against autodetachment higher than that of a bare CO2-, which results in the increasing stability of [(CO2)ROH](-) species. For n=2 the calculations predict the existence of two types of isomers having different degrees of the excess electron localization: CO2-. ROH(CO2) and C2O4-. ROH isomers. These "electronic isomers" are calculated to be close in energy, while their calculated vertical detachment energies (VDEs) differ by more than 1 eV. The ab initio results are discussed in comparison with recent experimental ones derived from photoelectron spectra of [(CO2)(n)ROH](-).