The thermal expansion coefficient (α) and calorimetric data were obtained as a function of temperature in order to clarify some of the significant variations reported with regard to these values in the literature. Stoichiometric and off-stoichiometric compositions of Ni3Al alloys (with and without boron addition) were investigated. Dilatometric experiments were performed on all the alloys and the α values were estimated over the temperature range from ambient to 1000°C. Two runs were made on each sample under different initial conditions and differences in α values were noticed. The results were analysed based on our earlier X-ray diffraction results. Additional isothermal dilatometric tests were also carried out and a significant volume change was noticed (0.45% contraction) when the alloy quenched from 1000°C was heated to 600°C and held for a long duration. The calorimetric data were obtaindd over the same range of temperature and enthalpy changes, though less distinct, were noticed at around 360, 660 and 900°C. The variations seen further augment our earlier results on the instability of the L12 structure and the existence of a structural transformation.