Geopolymer prepared from solid waste is a high value-added means. However, when used alone, the geopolymer produced by phosphogypsum has the risk of expansion cracking, while the geopolymer of recycled fine powder has high strength and good density, but its volume shrinkage and deformation are large. If the two are combined, the synergistic effect of the phosphogypsum geopolymer and recycled fine powder geopolymer can realize the complementarity of advantages and disadvantages, which provides a possibility for the preparation of stable geopolymers. In this study, the volume stability, water stability and mechanical stability of geopolymers were tested, and the stability synergy mechanism between phosphogypsum, recycled fine powder and slag was analyzed by micro experiments. The results show that the synergistic effect of phosphogypsum, recycled fine powder and slag can not only control the production of ettringite (AFt) but also control the capillary stress in the hydration product, thus improving the volume stability of the geopolymer. The synergistic effect can not only improve the pore structure of the hydration product but also reduce the negative impact of calcium sulfate dihydrate (CaSO4∙2H2O), thus improving the water stability of geopolymers. The softening coefficient of P15R45 with a 45 wt.% recycled fine powder content can reach 1.06, which is 26.2% higher than P35R25 with a 25 wt.% recycled fine powder content. The synergistic work reduces the negative impact of delayed AFt and improves the mechanical stability of the geopolymer.