Researchers are continuously seeking to develop new materials to protect against inclement weather and thus optimize energy efficiency in housing. This research aimed to determine the influence of corn starch percentage on the physicomechanical and microstructural properties of a diatomite-based porous ceramic. The starch consolidation casting technique was applied to fabricate a diatomite-based thermal insulating ceramic with hierarchical porosity. Diatomite mixtures with 0%, 10%, 20%, 30%, and 40% starch were consolidated. The results show that starch content significantly influences apparent porosity, and this, in turn, influences several parameters, such as thermal conductivity, diametral compressive strength, microstructure, and water absorption of diatomite-based ceramics. The porous ceramic processed by the starch consolidation casting method corresponding to the mixture of diatomite with 30% starch obtained the best properties, with a thermal conductivity of 0.0984 W/m·K, an apparent porosity of 57.88%, a water absorption of 58.45%, and a diametral compressive strength of 35.18 kg/cm2 (3.45 MPa). Our results reveal that the diatomite-based ceramic thermal insulator obtained by starch consolidation is effective for use on roofs to improve thermal comfort in dwellings located in cold regions.