This paper aims to experimentally and numerically probe thermo-mechanical coupling behaviors of 3D4D (three-dimensional four-directional) braided composite I-beam under four-point flexure. An improved algorithm based on thermo-mechanical coupling constitution model, and mixed failure criterion are devised for modeling thermo-mechanical coupling failure process of 3D4D braided composite I-beam under four-point flexure. Quasi-static four-point flexure tests are, respectively, performed on 3D4D braided composite I-beam at RT (room temperature), −50 ° C and 85 ° C , and mechanical behaviors and failure mechanisms are analyzed and discussed from experiment results. To validate the aforementioned model and algorithm, novel global-local FE (finite element) model is generated and integrated with new algorithm for modeling failure process of 3D4D braided composite I-beam under four-point flexure at three temperatures, and numerical predictions agree well with experimental findings, demonstrating the effective and rational use of the proposed model in the paper.