The HCl salt of hexaamidocyclotriphosphazatriene (HACTP) shows much of the characteristics of the well-established family of solid superionic conductors. The key feature revealing this trend is a Cole-Cole Z"-Z' dependence tending sharply to a low resistance, especially above 343 K far below the decomposition temperature, a three orders of magnitude rise in the d.c. (10(-4)-10(-1) Omega(-1) cm(-1)) and a.c. (10(-7)-10(-4) Omega(-1) cm(-1)) conductivity, a low ionic relaxation energy of 0.16 eV and a high capacitance of 0.1 F. The electric permittivity loss shows evidence of significant contribution from d.c. conduction. At the molecular scale, the origin of these peculiar features is assigned to a thermally induced structural shift in the HACTP-HCl ring from the puckered C-3v to the higher D-3h symmetry. The thermally induced planar ring supports a better orientation and hence interaction of the conduction ions with the phosphazene ring in the solid state. This structural shift is explicit in a DTA-detected solid-state phase transition activated at 343 K and optimized at 443 K prior to the melting at 513 K and is probed, using structure probe solid state PT-LR (in the same temperature range as the a.c.-conductivity) and H-1 NMR in solution. Spectral correlation of solid state FT-IR and solution H-1 NMR is necessarily made for distinguishing solid state from intrinsic phenomena.