Photoluminescent (PL) layers and electroluminescent (EL) systems have gained significant attention for their applications in constructing flat panels, screen monitors, and lighting systems. In this study, we present a groundbreaking approach to fabricating temperature sensors using barium-calcium zirconium titanate (BCZT) with thermo-optic properties, leading to the development of opto-thermal sensors for electric vehicle battery packs. We prepared zinc sulfide (ZnS) fluorescent films on BCZT ceramics, specifically two optimal compositions, BCZT0.85 (Ba0.85Ca0.15Zr0.1Ti0.9O3) and BCZT0.9 (Ba0.9Ca0.1Zr0.1Ti0.9O3), via the solid-state reaction method for the dielectric layer. The BCZT powders were calcined at varying temperatures (1200 and 1250 °C) and dwell times (2 and 4 h). The resulting phase formation and microstructure characteristics were analyzed using X-ray diffraction and scanning electron microscopy, respectively. Our investigation aimed to establish a correlation between the dielectric behavior and optical properties to determine the optimal composition and conditions for utilizing BCZT as thermal detectors in electric vehicle battery packs. All BCZT powders exhibited a tetragonal phase, as confirmed by JCPDS No. 01-079-2265. We observed an increase in the dielectric constant with higher calcining temperatures or longer dwell times. Remarkably, BCZT0.85 ceramic sintered at 1250 °C for 4 h displayed the highest dielectric constant of 15,342, establishing this condition as optimal for preparing the dielectric film with a maximum dielectric constant of 42. Furthermore, we investigated the temperature-dependent electroluminescence intensity of the samples, revealing a significant enhancement with increasing temperature, reaching its peak at 80 °C. Additionally, we observed a positive correlation between electroluminescence intensity and dielectric constant, indicating the potential for improved opto-thermal sensors. The findings from this study offer promising opportunities for the development of advanced opto-thermal sensors with potential applications in electric vehicle battery packs. Our work contributes to the expanding field of photoluminescent and electroluminescent systems by providing novel insights into the design and optimization of efficient and reliable sensors for thermal monitoring in electric vehicle technologies.