The burgeoning field of ionic liquids (in the current sense of low-melting liquids (T-m < 100 degrees C) consisting only of ions), has been dominated by liquids containing organic molecular cations. Although a few cases of all-inorganic ionic liquids are known, the field is relatively unexplored. As in the case of the organic cation salts, the inorganic ionic liquids can have aprotic, protic, and solvate cases, and can also be mixed with low melting alkali salts to give mixed alkali-molecular inorganic ionic liquid systems. Here we explore the interesting properties of (i) a low-melting alkali bromoaluminate, NaAl2Br7, which exhibits huge alkali cation decoupling in the crystalline state (such that there is very little change in conductivity on fusion) and (ii) its mixture with the low-melting inorganic ionic liquid [PBr4+][Al2Br7-]. The structures and ionicities are confirmed by Walden plots and by P-31 and Al-27 NMR spectroscopy. (C) 2017 The Electrochemical Society. All rights reserved.