Plastic crystals as a class are of much interest in applications as solid state electrolytes for electrochemical energy conversion devices. A subclass exhibit very high protonic conductivity and its members have been investigated as possible fuel cell electrolytes, as first demonstrated by Haile’s group in 2001 with CsHSO4. To date these have been inorganic compounds with tetrahedral oxyanions carrying one or more protons, charge-balanced by large alkali cations. Above the rotator phase transition, the HXO4- anions re-orient at a rate dependent on temperature while the centers of mass remain ordered. The transition is accompanied by a conductivity "jump" (as much as four orders of magnitude, to ~ 10 mScm-1 in the now-classic case of CsHSO4) due to mobile protons. These superprotonic plastic crystals bring a “true solid state” alternative to polymer electrolytes, operating at mild temperatures (150-200ºC) without the requirement of humidification. This work describes a new class of solid acids based on silicon, which are of general interest. Its members have extraordinary conductivities, as high as 21.5 mS/cm at room temperature, orders of magnitude above any previous reported case. Three fuel cells are demonstrated, delivering current densities as high as 225 mA/cm2 at short-circuit at 130ºC in one example and 640 mA/cm2 at 87ºC in another. The new compounds are insoluble in water, and their remarkably high conductivities over a wide temperature range allow for lower temperature operations, thus reducing the risk of hydrogen sulfide formation and dehydration reactions. Additionally, plastic crystals have highly advantageous properties that permit their application as solid state electrolytes in lithium batteries. So far only doped materials have been presented. This work presents for the first time non-doped plastic crystals in which the lithium ions are integral part of the structure, as a solid state electrolyte. The new electrolytes have conductivities of 3 to 10 mS/cm at room temperature, and in one example maintain a highly conductive state at temperatures as low as -30oC. The malleability of the materials and single ion conducting properties make these materials highly interesting candidates as a novel class of solid state lithium conductors.