Ion association of the ionic liquid [bmim][Cl] in acetonitrile and in water was studied by dielectric spectroscopy for salt concentrations c ≤ 1.3 M at 298.15 K and by measurement of molar electrical conductivities, Λ, of dilute solutions (c ≤ 0.006 M) in the temperature range 273.15 ≲ T/K ≤ 313.15. Whilst acetonitrile solutions of [bmim][Cl] exhibit moderate ion pairing, with an association constant of K^o _A ≈ 60 M⁻¹ and increasing with temperature, [bmim][Cl] is only weakly associated in water (K^o _A ≈ 6 M⁻¹) and ion pairing decreases with rising temperature. Only contact ion pairs were detected in both solvents. Standard-state enthalpy, entropy and heat capacity changes of ion association were derived, as well as the activation enthalpy of charge transport and the limiting conductivity of the cation, λ^∞ ([bmim]⁺). These data, in conjunction with effective solvation numbers obtained from the dielectric spectra, suggest that the solvation of [bmim]⁺ is much weaker in water than in acetonitrile.