A series of dissymmetric gemini surfactants with the general formula [C12H25(CH3)(2)N(CH2)(s)N(CH3)(2)C14H29]Br-2 designed as 12-s-14, where s = 2, 6, and 10, were synthesized and their physicochemical properties investigated. The effect of spacer length on Krafft temperature, adsorption at the air/solution interface, and association in aqueous solution was studied by tensionnetry, conductometry, and cryo-transmission electron microscopy. The Krafft temperature was found to increase linearly with spacer length. In the submicellar concentration range the dissymmetric 12-s-14 surfactants display ion pairing and premicellar association. Adsorption at air/solution interfaces and micellization in aqueous solution are similar to the behaviour of their symmetric counterparts and depend strongly on spacer length. (C) 2004 Elsevier Inc. All rights reserved.