Conduction mechanisms in solid polymer electrolytes of Li ion batteries have always been a concern due to their theoretical limitation in conductivity value. In an attempt to increase the ionic conductivity of solid state electrolytes, used in lithium ion secondary batteries (LiBs), we studied the synthesis and conductive properties of a low molecular weight cyclic organoboron crystalline electrolyte. This electrolyte was expected to show better electrochemical properties than solid polymer electrolytes. The electrolyte was doped with LiTFSI salt via two different methods viz. (1) facile grinding of the crystalline sample with lithium salt under a nitrogen atmosphere and (2) a conventional method of solvent dissolution and evaporation under vacuum. The electrochemical properties were studied under specific composition of Li salt. The presence of crystallinity in the electrolyte can be considered as an important factor behind the high ionic conductivity of an all solid electrolyte of this type. Charge–discharge properties of the cell using the electrolyte were investigated in anodic half-cell configuration.