In the field of high-performance cementitious composites, the application of textile-reinforced concrete (TRC) has emerged as a promising alternative for retrofitting and producing new structural components. Although TRC composites hold potential, they often exhibit poor performance under serviceability conditions. Addressing this limitation requires applying innovative techniques, such as prestressing, to utilise the full potential of TRC composites. A comprehensive understanding of the prestressing effect on the flexural response is crucial for successful design and application. The investigation focuses on key parameters, including prestressing level, prestressing release time, and matrix age, and their influence on the bond and flexural behaviour of basalt textile-reinforced concrete (PTRC) thin slabs. Test results indicate that prestressing considerably influences the structural response. Prestressing led to an enhanced cracking behaviour and load-bearing capacity with the increase in prestress level and release time. This study contributes valuable insights for optimising the performance of prestressed TRC materials, addressing a critical need in the field of TRC composite materials.