With a growing interest on inorganic ceramics based solid-state electrolytes for all-solid-state batteries, there is a need to maximise their density to optimise electrochemical performance and fuel impermeability. In this paper, we demonstrate the sensitivity of terahertz time-domain spectroscopy (THz-TDS) combined with effective medium theory to quantify the porosity or density of sodium superionic conductor (NaSICON)-based solid-state electrolyte (SSEs) pellets prepared at densities in the range of 2.2–2.9 g cm−3, corresponding to 50–90 % relative densities sintered at 900–1150 °C. The results of which, have been validated against complementary Archimedes analysis and mercury porosimetry highlighting the potential of THz-TDS for rapid, contactless, non-destructive electrolyte characterisation.