Low melting point alloy is a potential high-temperature heat transfer medium because of the high thermal conductivity, low solidus temperature and wide range of use temperature. Consequently, we investigated the possibility of using Sn–Bi–Zn–Ga alloys as heat storage and heat transfer material. Moreover, we investigated the microstructure and phase compositions by electron probe micro-analysis (EPMA) and X-ray diffusion (XRD). Results show that the new structures and phases are formed in the alloy matrix with Ga additions, which lead to the improvement of the thermal properties. An extensive thermophysical characterization of the Sn–Bi–Zn–Ga alloys has been performed by differential scanning calorimeter (DSC) analysis. The addition of Ga lowers the peak temperature and increases the heat capacity of the alloys. The thermal expansion of the test alloys increases with increasing temperature and the densities decreases with Ga additions. As the density, specific heat capacity and thermal diffusivity change with temperature and physical state, the thermal conductivity of the alloys first decreases and then increases. These results demonstrate the feasibility of using Sn–Bi–Zn–Ga alloys as the high-temperature heat transfer fluid.