The present investigation focuses on understanding the structure–electric conductivity correlation in NASICON-type LiSn$_2$(PO$_4$)$_3$ (LSP) powders prepared via solid-state reaction method. LSP powders synthesized at different temperatures were characterized for their structural and electrical properties using lab source powder X-ray diffraction (XRD), high-resolution synchrotron X-ray diffraction (SXRD) and complex impedance spectroscopy. LSP powders prepared in 900–1000°C temperature crystallize in triclinic structure (space group, P $\bar{1}$) along with the small amount of SnO$_2$ (P4$_2$/mnm) impurity phase. Samples prepared at temperatures in 1050–1250°C range showed a mixed rhombohedral (R $\bar{3}$c) and triclinic structure with the fraction of the triclinic phase decreasing with an increase in calcination temperature. On further increase in the calcination temperature to 1300°C, LSP transformed to the rhombohedral structure. Moreover, temperature-dependent SXRD confirmed that the LSP powder exhibits a martensitic behaviour, where a pure triclinic structure transforms into a pure rhombohedral phase at 170°C and retains a partial rhombohedral phase on cooling back to room temperature. The highest value of conductivity was found to be ${\sim}$1.06 ${\times}$ 10$^{–6}$ Scm$^{–1}$ for the LSP powder with triclinic structure calcined at 900°C, with an associated activation energy of ${\sim}$0.24 eV. Rhombohedral LSP calcined at 1300°C exhibits the lowest conductivity and highest activation energy at room temperature ${\sim}$1.12 ${\times}$ 10$^{–8}$ Scm$^{–1}$ and ${\sim}$0.39 eV, respectively. This decrease in conductivity for the supposedly highconducting rhombohedral phase is attributed to the drastic increase in the fraction of the SnO$_2$ impurity phase, as confirmed by the XRD analysis.