The influence of organic solvent was studied in the anion-exchange extraction of metal-chloride complexes, typically, 2(Q·C1)O+ (M2+)W+ 2(Cl−)W⇌ (Q2·MCl4)O(Q+: liquid anion-exchanger; M2+: divalent metal ion; subscripts o and w denote organic and aqueous phases, respectively). When protic solvents such as chloroform, pentanol, octanol, andp-nonylphenol, were used as diluent, a large depression in the metal extraction was observed as compared with the extraction using aprotic solvents. The inhibitory effect decreased in the order, phenol > alcohol > chloroform, which was accounted for on the basis of protic solvation or hydrogen-bonding interaction to anionic species by these solvent molecules. Thus, strongly hydrophilic anion (chloride) is stabilized via “protic solvation”, whereas weakly hydrophilic or rather hydorphobic anion (metal-chloride complex) is not much susceptible to such protic solvation effect. This difference renders the extraction of the latter type anions uneffective in protic solvent. Additive effect in organic solution of variouso-substitutedp-tert-octylphenols further demonstrated this concept of “protic solvation effect”. Further, the extraction selectivity induced by such protic solvation was applied to liquid-membrane transport phenomena of anionic species. A new possibility in the separation among anions was discussed.