Although fly ash foam concrete (FAFC) is lightweight, heat-retaining, and insulating, its application options are constrained by its weak construction and short lifespan. The effects of various dosage ratios of the foaming agent (i.e., hydrogen peroxide), silica fume, and polypropylene fiber on the dry density, compressive strength, thermal insulation performance, pore structure parameters, and durability of FAFC were analyzed in this study, which sought to address the issues of low strength and low durability of FAFC. According to the findings, there is a negative correlation between the amount of hydrogen peroxide (as the foaming agent) and compressive strength, and, as the silica fume and polypropylene fiber (PP fiber) content rise, the strength will initially rise and then fall. The distribution of pore sizes gradually shifts from being dominated by small pores to large pores as the amount of foaming agent increases, while the porosity and average pore size gradually decrease. When the hydrogen peroxide content is 5%, the pore shape factor is at its lowest. The pore size distribution was first dominated by a small pore size and thereafter by a large pore size when the silica fume and PP fiber concentration increased. Prior to increasing, the porosity, average pore size, and pore shape factor all decreased. Additionally, the impact of PP fiber on the freeze–thaw damage to FAFC was also investigated at the same time. The findings indicate that the freeze–thaw failure of FAFC is essentially frost heave failure of the pore wall. The use of PP fiber is crucial for enhancing FAFC’s ability to withstand frost. The best frost resistance is achieved at 0.4% PP fiber content. In conclusion, the ideal ratio for overall performance was found to be 5% hydrogen peroxide content, 4% silica fume content, and 0.1% polypropylene fiber content. The results obtained could be applied in different fields, such as construction and sustainable materials, among others.