This paper aims to demonstrate the self-protection and self-sensing functionalities of self-compacted concrete (SCC) containing carbon nanotubes (CNT) and carbon microfibers (CMF) in a hybrid system. The ability for self-sensing at room temperature and that of self-protection after thermal fatigue cycles is evaluated. A binder containing a high volume of supplementary mineral additions (30%BFSand20%FA) and different type of aggregates (basalt, limestone, and clinker) are used. The self-diagnosis is assessed measuring electrical resistivity (ER) and piezoresistivity (PZR) in compression mode within the elastic region of the concrete. Thermal fatigue is evaluated with mechanical and crack measurements after heat cycles (290–550 °C). SCC withstands high temperature cycles. The protective effect of the hybrid additive (CNT+CMF) notably diminishes damage by keepinghigher residual strength and lessmicrocracking of the concrete. Significant reductions in ER are detected. The self-diagnosis ability of functionalized SCC isconfirmed with PZR. A content of the hybrid functional additive (CNT+CMF) in the percolation region is recommended to maximize the self-sensing sensitivity. Other parameters as sample geometry, sensor location, power supply, and load level have less influence.