Lithium-ion batteries (LiBs) are widely used as energy storage systems (ESSs). The biggest challenge they face is retaining intrinsic health under all conditions, and understanding internal thermal behaviour is crucial to this. The key concern is the potentially large temperature differences at high charge/discharge rates. Excess heat created during charge/discharge will accelerate irreversible aging, eventually leading to failure. As a consequence, it is important to keep battery states within their safe operating range, which is determined by voltage, temperature, and current windows. Due to the chemically aggressive and electrically noisy environment, internal temperature measurement is difficult. As a result, non-invasive sensors must be physically stable, electromagnetic interference-resistant, and chemically inert. These characteristics are provided by fibre Bragg grating (FBG) sensors, which are also multiplexable. This review article discusses the thermal problems that arise during LiB use, as well as their significance in terms of LiB durability and protection. FBG-based sensors are described as a technology, with emphasis on their importance for direct temperature measurement within the LiB cell.