Cement-based materials are usually not exposed to an independent deterioration process but are exposed to a combination of mechanical load and environmental effects. This paper reports the frost resistance durability of strain-hardening cement-based composites (SHCC) under combined flexural loading at different levels and under chloride attack. The loss of mass, dynamic elastic modulus, and microstructure characteristics of SHCC specimens were determined, and the influence of loading level on frost resistance was analyzed. In addition, the effect of freeze–thaw action on the flexural performance and diffusion properties of chloride in SHCC under the combined loads was investigated. The results show that the process of degradation was accelerated due to the simultaneous action of flexural loading and freeze–thaw cycles in the chloride environment, and SHCC suffered more serious damage at a higher loading level. However, flexural strength decreased by only 13.87% after 300 freeze–thaw cycles at load level S = 0.36. The diffusion properties of chloride in SHCC under constant flexural loading were affected by the freezing and thawing cycle. The free chloride concentration C_f increased with the development of freezing and thawing at the same diffusion depth, and a bilinear relationship was found between the chloride diffusion coefficient D_c and the number of freeze–thaw cycles.