Fire is one of the most unfavorable conditions that cement-based composites can face during their service lives. The uniaxial tensile and flexural tensile properties of the steel-polyvinyl alcohol fiber-calcium carbonate whisker (CW) multi-scale fiber reinforced cement matrix composites (MSFRCs) under high temperatures are studied, including strength, deformation capacity, energy dissipation capacity, and its ability to be assessed through the empirical calculation method. The study showed that with the increase of the treatment temperature, the MSFRC residual bending strength, bending toughness, and tensile strength decreased overall, but the decline was slow at 600 °C. The peak flexural deflection and peak tensile strain of MSFRC first reduced and then increased with the increase of the temperature. As the temperature increased, the nominal stiffness of MSFRC bending and straight gradually reduced, and the rate of decline was faster than that of its strength. However, the uniaxial tensile properties were more sensitive to the temperature and degraded more rapidly. A quantitative relationship was established between MSFRC residual bending, tensile strength, and temperature. A comparison with existing research results shows that MSFRC has achieved an ideal effect of high temperature resistance. The multi-scale hybrid fiber system significantly alleviates the deterioration of cement-based composite’s mechanical properties under high temperatures. With the help of an optical microscope and scanning electron microscope (SEM), the high temperature influence mechanism on the uniaxial tensile and flexural properties of MSFRC was revealed.