To investigate the effects of nano-SiO2 (NS) and polyvinyl alcohol (PVA) fibers on the durability and mechanical properties of cementitious composites subjected to saline freeze–thaw cycling, a series of PVA fiber-reinforced cementitious composite (PFRCC) specimens were prepared using various fiber contents, and a series of NS and PVA fiber-reinforced cementitious composite (NPFRCC) specimens were prepared using various combinations of NS and fiber contents. Durability and fracture toughness tests were subsequently conducted on the specimens after different numbers of saline freeze–thaw cycles. The results indicate that the degradation of material properties can be divided into slow and accelerated damage stages before/after 50 freeze–thaw cycles. The durability and fracture toughness of the specimen series tended to increase, then decrease with increasing NS and PVA contents, suggesting optimum levels. When the PVA fiber content was 0.5%, PFRCC specimens had the best durability after saline freeze–thaw cycles; when the NS and PVA fiber contents were 1.0% and 0.5%, respectively, NPFRCC specimens had the best durability and fracture properties, and the initiation toughness, destabilization toughness, and fracture energy after 100 saline freeze–thaw cycles were 120.69%, 160.02%, and 451.31%, respectively. The results of this study may guide future exploration of the durability and mechanical properties of concrete subjected to freeze–thaw action.