Abstract Conductivities of some tetraalkylammonium halides, viz. tetramethylammonium iodide (Me 4NI), tetraethylammonium bromide (Et 4NBr), tetraethylammonium iodide (Et 4NI), tetra- n-propylammonium bromide (Pr 4NBr), tetra- n-butylammonium bromide (Bu 4NBr), tetra- n-butylammonium iodide (Bu 4NI) and tetra- n-heptylammonium bromide (Hp 4NBr) were measured at 298.15 K in 1,3-dioxolane which has a low permittivity ( ε = 7.13). A minima in the conductometric curves (molar conductance, Λ vs. square root of concentration, √ c) was observed for concentrations which were dependant upon both the salt and the solvent. The observed molar conductivities were explained by the formation of ion-pairs (M + + X − ↔ MX, K P) and triple-ions (2M + + X − ↔ M 2X +; M + + 2X − ↔ MX 2 −, K T). A linear relationship between the triple-ion formation constants [log ( K T/ K P)] and the salt concentrations at the minimum conductivity (log C min) was given for all the salts in 1,3-dioxolane. The formation of triple-ions might be attributed to the ion sizes in solutions in which Coulombic interactions and non-Coulombic interactions act as the main forces between the ions (R 4N +…..X −).