In the present work the thermal conductivity of 29 samples of clay bricks was measured and the correlations of the thermal performance with the compositional, physical, and microstructural features of products were investigated. The results obtained directed our attention toward a better understanding of the role played by some parameters (i.e., mineralogical components and pore size distribution), other than bulk density, in improving or depressing the insulating properties of bricks. Among them, the unfavorable role of quartz, Ca-rich silicates, and amorphous phase came out, while the role of pore size and specific surface should be more accurately evaluated in the structural design of materials