This experimental study investigates the potential of chemical prestressing technology to improve the structural performance of carbon textile-reinforced concrete plates reinforced with varying ratios of carbon textile reinforcement. For this aim, 30 concrete plates of dimensions 1000 mm × 160 mm × 30 mm were cast. Fifteen of the plates were made using normal concrete to serve as the control group, while the remaining fifteen were made of expansive concrete. Each group was further subdivided into five subgroups depending on the reinforcement ratio. The distributed fibre optic sensor (DFOS) technology was used to track the development of the expansion/shrinkage strains for 90 days. Moreover, the influence of expansion on the strength of the concrete was also studied during this period at key dates. In the end, all the plates were tested till failure under a four-point bending test. The findings demonstrated that the developed expansive concrete mixture achieves stable and consistent expansion with minimal damage to the concrete strength. Moreover, a full bond was established between the textile reinforcement and the expansive concrete, enabling full transfer of the expansion strain and generating significant tensile stresses within the reinforcement, exceeding 480 MPa. Lastly, the bending tests showed that chemical prestressing improves the structural performance significantly by increasing the cracking resistance and stiffness as well as enhancing the strain distribution, and thus leading to higher ultimate failure loads. Additionally, a Eurocode-based flexural behaviour model was also developed to predict the flexural behaviour of the chemically prestressed CTRC plates. The model has shown to yield good agreement with the experimental results.