The infrared photodissociation spectra of [(CO2)(n)(CH3OH)(m)](-) (n = 1-4, m = 1, 2) are measured in the 2700-3700 cm(-1) range. The observed spectra consist of an intense broad band characteristic of hydrogen-bonded OH stretching vibrations at approximate to 3300 cm(-1) and congested vibrational bands around 2900 cm(-1). No photofragment signal is observed for [(CO2)(1,2)(CH3OH)(1)](-) in the spectral range studied. Ab initio calculations are per-formed at the MP2/6-311++G** level to obtain structural information such as optimized structures, stabilization energies, and vibrational frequencies of [(CO2)(n)(CH3OH)(m)](-). Comparison between the experimental and the theoretical results reveals the structural properties of [(CO2)(n)(CH3OH)(m)](-): (I) the incorporated CH3OH interacts directly with either CO2- or C2O4- Core by forming an O-H-O linkage; (2) the introduction of CH3OH promotes charge localization in the clusters via the hydrogen-bond formation, resulting in the predominance of CO2-center dot(CH3OH)(m)(CO2)(n-1) isomeric forms over C2O4-center dot(CH3OH)(m)(CO2)(n-2); (3) the hydroxyl group of CH3OH provides an additional solvation cite for neutral CO2 molecules.