The electrical conductivity, density and diffusion coefficients of trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)amide ([P66614][NTf2]) ionic liquid and its binary solutions in acetonitrile, propionitrile, dimethyl and diethyl carbonates were measured in the temperature range of 293-348 K. The electrical conductivity - ionic liquid mole fraction dependencies for the binary solutions were fitted with the empirical Casteel-Amis equation. The temperature dependencies of electrical conductivity were analyzed using the Arrhenius, Litovitz and Vogel-Fulcher-Tammann approaches. The dependences of the Arrhenius activation energy and pre-exponential factor on the mole fraction of ionic liquid in the solutions were fitted with the empirical equations proposed in the literature. The thermo-gravimetric analysis combined with mass spectrometry demonstrated the high thermal stability of [P66614][NTf2] up to 600 K. At higher temperatures the decomposition of [P66614][NTf2] proceeded via the elimination of alkyl radicals as a result of the nucleophilic attack of reactive intermediates to the [P66614]+ cation with the formation of trialkylphosphines. The activation energies of the thermal destruction of [P66614][NTf2] were calculated using the Kissinger equation and non-linear integral isoconversional model.