Current conventional cement materials are no longer able to meet the actual usage needs of geotechnical engineering. In order to improve the workability of cement materials used in geotechnical, transportation, and mining engineering, it is necessary to improve the formulation of cement materials. Polypropylene fibers (PVAF), polyvinyl alcohol fibers (PPF), and fly ash (FA) are used in this study to modify Portland–sulfoaluminate composite cement to improve the workability of the cement material system. Meanwhile, the microstructure that affects the system performance was also studied. The research results indicate that adding FA to the composite cement system can improve its fluidity. In the later stage of hydration, due to the volcanic ash reaction, the production of hydration products will increase, but it will not affect the type of hydration products. Adding PPF-PVAF can effectively improve the strength performance of the cement system. The compressive strength reached 24.61 MPa after 28 days of curing, which was 13.8% higher than the blank sample. Adding calcium hydroxide powder and FA to the system can improve the fluidity of the cement system to a certain extent and positively impact the later strength. After 28 days of curing, the compressive strength of experimental group 9 reached 30.21 MPa, which increased by 70.5% compared to after 7 days These results were found at the microscopic level, based on analyses via XRD, TG, and SEM. The Mix-EXP cured for 28 days has better hydration product content and composition arrangement of cement slurry than the O-S-C cured for 28 days.