Qualitative and quantitative analyses of molecular interaction prevailing in ionic salt-organic solvent media, probed by electrical conductances have been reported. Tetrabutylammonium tetrafluoroborate [Bu4NBF4] in acetonitrile (CH3CN), methanol (CH3OH), dimethylsulfoxide (DMSO) and 1,3-dioxolane (1,3-DO) have been studied at 298.15 K. The extent of interaction is expressed in terms of the association constant (K-A) and shows the interaction to be a function of viscosity. Limiting molar conductances (Delta(o)), association constants (K-A), and the association diameter (R) for ion-pair formation have been analyzed using the Fuoss conductance-concentration equation (1978). The observed molar conductivities were explained by the formation of ion-pairs (M++X <-> MMX, K-P) and triple-ions (2M(+) + X <-> M2X+; M+ + 2X - <-> MX2 , K-T). The Walden product is obtained and discussed. The deviation of the conductometric curves (Lambda vs c(1/2)) from linearity for the electrolyte in 1,3-dioxolane indicates triple-ion formation, and therefore the corresponding conductance data have been analyzed by using the Fuoss-Kraus theory of triple-ions. The limiting ionic conductances (Lambda(o)) have been calculated from the appropriate division of the limiting molar conductivity value of tetrabutylammonium tetraphenylborate [Bu4NBPh4] as the "reference electrolyte" method along with a numerical evaluation of ion-pair and triple-ion formation constants (K-P - K-A and K-T). The results have been interpreted in terms of solvent properties and configurational theory. (C) 2013 Elsevier Ltd. All rights reserved.