In this work we aimed to determine the ions association and solvation in electrolytes comprised of NaPF6 in binary EC:PC, and ternary 5EC:3PC:2DEC carbonate solvents. We studied their local and bulk transport properties through multi-Nuclear (1H, 19F and 23Na) Magnetic Resonance spin-lattice relaxation time (T1 ) and self-diffusion coefficient (D) measurements. These studies were complemented with ionic conductivity and solution viscosity measurements. Results show several interesting features. Firstly, the Walden Product – which relates the molar conductivity and viscosity through a temperature-dependent constant – showed a dependence on temperature (see Figure 1). This suggested the dissociation of NaPF6 is dependent on temperature and is lower for the less polar electrolytes. Secondly, the sodium ions are preferentially solvated by PC molecules over EC. Thirdly, significant cation-anion association was observed for the less polar electrolytes. Lastly, this association was independent of temperature indicating that the temperature dependence of the Walden Product is primarily due to that of the viscosity. These results can aid in the improvement of ‘beyond lithium ion’ electrolytes for energy storage applications. Figure 1