The binary mixtures of Neopentanol (NPOH) with tert-Butyl chloride (TBC) and Carbon tetrachloride (CTC), have been studied using Differential Scanning Calorimetry, Dielectric spectroscopy and X-ray diffraction techniques. The results indicate the formation of the solid solutions. The crystalline solid thus formed is found to be orientationally disordered and supercools easily to form glassy crystal for mole fraction of NPOH in the range of 0.7-0.9. The T-g values are in the range of 140-147 K. In the dielectric study, a primary alpha-process and two sub-T-g processes are found for TBC-NPOH, whereas for CTC-NPOH only one sub-T-g process is found: The dielectric spectra of alpha- process follows the Havriliak-Negami equation. The sub-T-g processes follow the Cole-Cole equation, and are found to be of Johari-Goldstein type, indicating intermolecular nature. (C) 2016 Elsevier B.V. All rights reserved.