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 330K by precision adiabatic vacuum calorimetry. The experimental data were used to calculate standard thermodynamic functions, namely the heat capacity C ° p ( T ) , enthalpy H ° ( T ) − H ° ( 0 ) , entropy S ° ( T ) − S ° ( 0 ) and Gibbs function G ° ( T ) − H ° ( 0 ) , for the range from T →0 to 670K. Raman and IR investigations have also been performed. The high-temperature X-ray diffraction method was used for the determination of thermal expansion coefficients.