An effect of metal cations on betanin stability was investigated in aqueous and organic-aqueous solutions. The presence of organic solvents (methanol, ethanol, and acetonitrile) affects substantially the pigments decomposition in acidic media induced by metal cations whose degrading action in such media is significantly higher than in aqueous solutions. The influence of Cu2+ on the stability was studied by spectrophotometry in more detailed manner, because of its ability to form complexes with betanin. The possibility of a complex formation between betanin and Ni2+ was also stated at pH 7–8; its relatively high stability in aqueous samples was observed. A presence of numerous products of betanin decomposition was detected in the wavelength range 380–500 nm in spectra obtained for most of metal cations investigated, especially for higher concentrations of the organic solvents.