In the present work temperature dependence of heat capacity of Li4/3Ti5/3O4 has been measured for the first time in the range from 6 to 330 K by precision adiabatic vacuum calorimetry. The experimental data were used to calculate standard thermodynamic functions, namely the heat capacity C-p degrees(T), enthalpy H degrees(T) - H degrees(0), entropy S degrees(T) - S degrees(0) and Gibbs function G degrees(T) - H degrees(0), for the range from T -> 0 to 670 K. Raman and IR investigations have also been performed. The high-temperature X-ray diffraction method was used for the determination of thermal expansion coefficients. (C) 2013 Elsevier B.V. All rights reserved.