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The CO adsorption on vanadium-doped gold clusters AunV with n = 1-14 is studied by density functional theory computations, using the BB95 and B3LYP functionals along with the cc-pVDZ-PP basis for metals and cc-pVTZ for non-metals. When both Au and V sites are exposed, CO adsorption on V is thermodynamically favorable because with partially filling d orbitals vanadium is more willing to interact with CO empty or filled orbitals. When vanadium is confined inside a gold cage, the low-coordinated Au atoms become the preferred sites for CO attachment. The presence of V tends to reinforce CO adsorption as compared with the bare gold clusters. The diatomic AuV is predicted to have the largest CO adsorption affinity as it has a typical π-back donation bond. AunV-CO complexes typically have the larger CO binding energies and larger CO frequency shift than the isoatomic gold-carbonyl Aun+1-CO counterparts. [ABSTRACT FROM AUTHOR]