Bolaform electrolytes have two ionic groups at both terminal groups and have been widely investigated. However, their effects on the binding of small molecules with water-soluble polymers and the dye sorption by films and fibers have been rarely studied. Recently, various bolaform electrolytes have been synthesized and their effects on the binding of acid dyes with poly(vinylpyrrolidone) (PVP) in aqueous solutions and the sorption of acid dyes by nylon 6 and silk have been investigated in detail. This paper reviews the behaviour of the bolaform electrolytes as the controller for the binding and the auxiliaries for the sorption (dyeing). The structural effects of the bolaform electrolytes (terminal and spacer groups) on the binding constants and the sorption parameters are successively reviewed.