Nucleophilic solvation is the interaction of electron-donor solvents with electron-deficient reagents. Electrophilic solvation is the related reverse interaction. Superelectrophilic solvation involves the interaction of electron-donating groups (ligands) of overall electron-deficient species (electrophiles) with strongly electron-acceptor superacids. It occurs with liquid superacids, on solid acids, and even in some enzymatic biological systems. Diminishing neighboring group participation of the electrophilic centers by the affected groups greatly enhances their electrophilic reactivities (superelectrophilic activation), resulting in unusual reactions of substantial interest. Representative examples of superelectrophilic solvation are discussed.