The tritium tagged water (HTO) exchange rates between water swollen Nafion-117 membrane and equilibrating water were measured to obtain self-diffusion coefficients of water (D-H2O(m)) in the membrane samples with several multivalent counterions, viz. Ba2+, Fe3+, La3+, Eu3+ and Th4+. The values of D-H2O(m) were obtained by analyzing the isotopic exchange rates profiles using an analytical solution of Fick's second law. The values of D-H2O(m) in these ionic forms of Nafion-117 membrane were found to be in the range of 1.8 x 10(-6) - 10(-6) cm(2)/s. The water uptake capacity in the membrane samples with multivalent counterions was also not found to vary significantly. Since diffusion of water occurs through water channels in the membrane, the narrow spread of D-H2O(m) values in membrane samples with multivalent counterions was attributed to nearly constant polymer volume fraction (V-p = 0.75 +/- 0.02) in the membrane. The comparison of D-H2O(m), values obtained in the present work with that reported for Nafion-117 membrane having same V-p (0.75) with Na+ counterions (2.85 x 10(-6) cm(2)/s) indicated that the self-diffusivity of water is higher in monovalent forms of membrane. D-H2O(m) represents tortuosity factor in membrane and hence it is dependent on V-p and microstructure of the membrane. Therefore, the slight difference in D-H2O(m) values in monovalent and multivalent forms of membrane with same V-p could be attributed to minor difference in transport channels of membrane in these forms of Nation-117 membrane. (c) 2006 Elsevier B.V. All rights reserved.