Lithium-ion batteries are currently the alternative of choice to overcome the increasing demand of energy. However, besides the scarcity of lithium and limited geolocation, it is believed that such batteries have already reached their maximum maturity. Sodium batteries emerge as an alternative to produce the new, so called, post-lithium batteries. In this study, we explore (i) the effect of sodium content and sintering temperature in solid electrolytes based in NASICON-type compounds and (ii) the use of two methodologies to obtain porous NASICON samples: application of natural substances and organic materials as pore-formers and freeze casting. The main purpose is the attainment of hybrid quasi-solid state electrolytes, with enhanced room temperature conductivity, based on porous ceramic electrolyte layers infiltrated with ionic liquids. Using this approach, porous samples with different microstructure and porous morphology and distribution were achieved, providing an enhancement in conductivity (ranging from 0.45 to 0.96 mS cm−1 at 30 °C) of one order of magnitude for infiltrated samples respect to pore-free samples. According to these results the porous NASICON might be considered as a functional macroporous inorganic separator that can act as a Na+ reservoir.