This research aims to reveal the effect of phosphorus slag (PS) admixtures on the properties and hydration mechanism of circulating fluidized bed fly ash (CFA)-based multi-solid waste cementitious material (CWM). The results indicate that PS as an admixture is more helpful for improving the performance of CWM systems compared with blast furnace slag with a high specific surface area (HBFS) and gasification slag (GS). In this work, CWM2 is prepared with 30 wt.% CFA, 10 wt.% red mud (RM), 20 wt.% blast furnace slag (BFS), 10 wt.% PS, and 30 wt.% cement clinker (CC). The compressive strength and expansion value of CWM2 are the optimal (51.15 MPa and 0.70 mm) when the mass ratio of (Ca + Na)/(Si +Al) is 0.84, which can meet the requirements of 42.5 fly ash Portland cement. In addition, the polymerization degree of CWM2-28 days is the optimum (51.57%) because [PO4] and [SiO4] combine to improve its polymerization structure. The main hydration products are C-S-H gel, C/N-A-S-H gel, and ettringite in CWM, which are conducive to improve the compactness of the micromorphology. In addition, the consolidation of Na, As, Cd, and Hg is promoted in CWM2 by physical encapsulation and charge balance, which meet the drinking water requirements of the World Health Organization (WHO). Therefore, this work provides a new idea for the application of PS as an admixture in CFA-based multi-solid waste cementitious material.