The fabrication of ceramic composites with low thermal expansion and excellent mechanical properties is essential for thermal barrier coating (TBC) applications. For this purpose, using the sol-gel process, novel ceramic composites were developed by combining varying weight percentages of β-spodumene (0–20 wt%) with zirconia toughened alumina (ZTA). The influence of β-spodumene addition on the densification, phase composition, microstructure, and mechanical, thermal, and fracture behavior of the studied composites was investigated experimentally and numerically. Increasing the β-spodumene content reduces the sintering temperature of the formed composites by 75 °C. Introducing 5 wt% β-spodumene to ZTA composite improves the densification process by serving as a mineralizer. X-ray diffraction (XRD) revealed that the t-m ZrO2 transformation was enhanced by increasing the β-spodumene content. The results demonstrated that composites with β-spodumene content of 5 wt% exhibited the best mechanical performance. The numerical prediction of fracture toughness agreed well with the experimental results for different composites.