Raman spectra were measured for the system consisting of a-Al20 z powder and aqueous electrolyte solution of LiNO3, NaNO3, CH~COOLi, and CH3COONa, in order to discuss a hetero-phase coexisting effect of the solid phase on the properties of the liquid phase. The Raman bands assigned to the stretching mode of OH2 at 2800-4000 cm "1 was distorted by the heterophase coexisting effect, and the distortion depended on the dissolved anionic species. The distortion for the system containing acetate anions, which have hydrophobic and hydrophilic groups, was different from those for the other systems, i.e. pure water and aqueous nitrate solutions as the liquid phase. The NO 3" symmetric stretching mode (v~) of nitrate anion at ca. 1045 cm ~, the COO stretching mode of (v~) at ca. 1415 cm -1, and the C-C stretching mode (v4) at ca. 925 cm 1 of acetate ion were also measured and the changes of their position are discussed. Each Raman band shifted and broadened with the content and specific surface area of the solid phase from the original position and shift for the bulk of each aqueous solution. It is suggested that the intra-molecular structure of ionic species is influenced by the existance of solid surface. The hetero-phase coexisting effects, caused by the solid phase, mainly depend mainly on the nature of anionic species in the system.