The relationship between structure and ion transport in liquid electrolyte solutions is not well understood over the whole concentration and temperature ranges. In this work, we have studied the ionic conductivity (κ) as a function of molar ratio (x) and Temperature (T) for aqueous solutions of salts with nitrate anion and different cations (proton, lithium, calcium, and ammonium) along with their liquid-solid phase diagrams. The connection between the known structural changes in the phase diagrams and the ionic conductivity isotherms is established with an insight on the conductivity mechanism. Also, known isothermal (κ vs. x) and iso-compositional (κ vs. T) equations along with a newly proposed two variables semi-empirical model (κ = f (x, T)) were fitted to the collected data to validate their accuracy. The role of activation energy in controlling ionic conductivity is discussed. This work brings us closer to the development of a phenomenological model to describe the structure and transport in liquid electrolyte solutions.