The thermo-mechanical behavior of masonry materials is investigated through an in-tegrated experimental testing and numerical modelling approach. The study focuses on the characterization of masonry under fire exposure, where coupled thermal and mechanical effects govern material response and failure mechanisms. A multi-scale framework is proposed to link physico-chemical transformations, material-level prop-erties, and structural-scale behavior. The experimental component includes full-scale fire-resistance tests on load-bearing masonry walls, providing temperature evolution, deformation histories, and observed damage patterns. These results enable the identi-fication of key mechanisms such as stiffness degradation, cracking, and the influence of thermal gradients on structural response. The experimental observations are used to support the development and calibration of numerical models capable of representing temperature-dependent behavior and strain-rate effects. In addition, non-destructive testing techniques are incorporated to relate internal damage to measurable diagnostic signals, enhancing material characterization and structural assessment. Although the present study is limited to structural-scale validation, the proposed approach demon-strates how combined experimental and numerical strategies can be used to develop consistent constitutive descriptions of masonry materials. The results contribute to improved understanding and modelling of engineering materials subjected to coupled thermo-mechanical loading.