The challenges for the use of the cross-laminated timber (CLT) system in the Brazilian agricultural market are significant. This study evaluated the thermal performance of fiber cement tiles associated with a CLT non-conventional structure compared to those of ceramic, fiber cement and aluminum roof tiles based on following thermal comfort indexes (i.e., black globe humidity index (BGHI), radiant heat load (RHL) and specific enthalpy) using physical conventional models of reduced-scale rural facilities under summer conditions. The non-conventional CLT model comprised closing walls and a lining that form a self-supporting structure with few air inlets. This model presented reduced thermal comfort indexes compared to the other conventional roofs. Moreover, the CLT model has an average black globe temperature (Tbg) of 32.9 °C, which was lower at all times compared to those of the other roofs. In conclusion, the roof with fiber cement tiles associated with the CLT structure exhibited the best performance in terms of thermal comfort, followed by the ceramic, fiber cement, and aluminum tiles. The study results allow a better understanding of the opportunities for CLT usage.