To address the mechanical deficiencies of traditional pervious concrete and promote its practical implementation, this study developed a high-performance pervious concrete model using conventional materials and methods, achieving a permeability coefficient of 4.5 mm/s with compressive and flexural strengths exceeding 45 MPa and 5 MPa, respectively. Central composite design (CCD) response surface methodology was employed to investigate the individual and synergistic effects of the water–cement ratio (W/C), nano-silica (NS), and carbon fibers (CF) on permeability, compressive strength, and flexural strength. Statistical models demonstrating prediction errors within 7% of experimental values were established, supplemented by a microstructural analysis of the concrete specimens. The results demonstrated that (1) the W/C ratio significantly influences overall performance; (2) NS enhances mechanical strength while reducing permeability, though excessive NS content induces weak interfacial zones that compromise strength; (3) CFs exhibit negligible impact on compressive strength but substantially improve flexural performance; and (4) significant synergistic interactions are present across W/C ratio, NS, and CFs concerning flexural strength parameters, while no significant interaction was observed for compressive strength.

To address the susceptibility of traditional concrete to explosive spalling and the lack of in situ damage-monitoring methods at high temperatures, in this study, a novel self-sensing, high-temperature-resistant Engineered Cementitious Composite (ECC) was developed. The matrix contains eco-friendly glass sand reinforced with a hybrid system of polypropylene fibers (PPFs) and carbon fibers (CFs). The evolution of mechanical properties and the multimodal self-sensing characteristics of the ECC were systematically investigated following thermal treatment from 20 °C to 800 °C. The results indicate that the hybrid system exhibits a significant synergistic effect: through PFFs’ pore-forming mechanism, internal vapor pressure is effectively released to mitigate spalling, while CFs provide residual strength compensation. Mechanically, the compressive strength increased by 51.32% (0.9% CF + 1.0% PPF) at 400 °C compared to ambient temperature, attributed to high-temperature-activated secondary hydration. Regarding self-sensing, the composite containing 1.1% CF and 1.5% PPF displayed superior thermosensitivity during heating (resistivity reduction of 49.1%), indicating potential for early fire warnings. Notably, pressure sensitivity was enhanced after high-temperature exposure, with the 0.7% CF + 0.5% PPF group achieving a Fractional Change in Resistivity of 31.1% at 600 °C. Conversely, flexural sensitivity presented a “thermally induced attenuation effect” primarily attributed to high-temperature-induced interfacial weakening. This study confirms that the “pore-formation” mechanism, combined with the reconstruction of the conductive network, governs the material’s macroscopic properties, providing a theoretical basis for green, intelligent, and fire-safe infrastructure.