In this paper, the influence of Nano-silica (NS) and Polyvinyl alcohol (PVA) fibers on the corrosion behavior of steel rebar embedded in high-volume fly ash cement mortars under accelerated chloride attack was studied by using an impressed voltage technique. The PVA fibers used were 1.0 vol.%, and two mass fractions of cement (50 and 60 wt.%) were replaced by fly ash. Four NS mass fractions (0, 0.5, 1.0, and 1.5 wt.%) were utilized in this paper. In addition, the mono and hybrid effects of NS and PVA on the mechanical properties and water absorption of mortar were also studied. The results showed that the incorporation of PVA and nano-SiO2 can improve the flexural and compressive strengths of high-volume fly ash mortar. Generally, the flexural and compressive strengths increased with the increase of nano-SiO2 content. Moreover, the incorporation NS can also reduce the capillary water–absorption rate of cement mortar. The impressed voltage corrosion test indicated that the composite incorporation of nano-SiO2 and PVA can significantly delay the deterioration process of steel bars in mortar, effectively reducing the steel rebar’s corrosion level and increasing the exposure time of the surface crack. With hybrid-incorporation 1.0 vol.% PVA and 1.0 wt.% nano-SiO2, the steel rebar had the lowest corrosion degree, which exhibited a mass loss of 49% and increased the broken time by 71% as compared to the control mortar.