Basalt fiber reinforced fly ash concrete (BFRFAC) is a new inorganic non-metal composite building material with superior mechanical performance, which can be extensively applied in the fields of bridge floors, pavements and other construction engineering projects. In the present paper, the freezing and thawing resistance performance of BFRFAC under corrosion conditions was studied in detail with the comparison to the Normal Concrete (NC). Experimental studies on the mass loss rate (MLR) in a non-corrosive environment, and the MLR as well as the relative dynamic modulus of elasticity (RDME) in chlorine corrosion, sulfate corrosion and the complex combined corrosion of chloride and sulfate solution were conducted through the quick freezing method. Further, the meso-structure of the fracture section in the composite material was scanned with the help of a scanning electron microscope (SEM) at amplified ×500, ×1,000 and ×1,500. The gripping effect between basalt fibers and substrate under the case of pull-out failure and fracture failure was quantitatively analyzed, which convincingly revealed the crack resistance, reinforcement and strengthening mechanisms of basalt fibers on concrete substrate. The research results indicated that RDME decreased and its decent rate became slower in turn when the composite material was exposed to freeze-thaw cycles in all the above four considered cases. Among them, in the case of the complex solution corrosion, the number of freeze-thaw cycles of BFRFAC was larger than 400. Compared to the NC, the BFRFAC cyclic lifespan could be extended effectively. In addition, the full play of fly ash activity and great filling effect enhanced the gripping effect between basalt fibers and concrete substrate. Therefore, it could effectively improve the freezing and thawing resistance damage capacity of BFRFAC.