The silica-alumina sol bonding agent, prepared by the sol gel route from ethyl silicate and aluminium isopropanol, was utilized in the refractory castables. The influence of structure on the heat transfer has been investigated using different sorts of refractory matrix. The results indicated that the heat conductivity of sol-gel bonded castables was considerably affected by their structure. The phase composition of matrix, porosity, pore size distribution and pore size structure were the most important factors. Thermal conductivity has been measured from the ambient temperature up to 1250 °C. The influence of crystalline phases and the glassy phase formation and the influence of the pore size distribution on the thermal conductivity were also described in this work.