Supersulfate cement (SSC) has received significant attention in the construction industry due to its extensive utilization of solid wastes and low carbon emissions. However, the low carbonation resistance and early strength of SSC greatly restricted its application, which was attributed to early insufficient alkalinity and slow hydration. Facilitating early hydration alkalinity is critical to promote early hydration and improve early performance for SSC. Thus, sodium aluminate (SA), an admixture with concentrations ranging from 0% to 4%, was adopted to enhance early alkalinity and investigate its impact on the initial hydration process. The results indicated that incorporating SA into SSC enhances its early performance by balancing high alkalinity and AFt stability. The addition of 2% SA accelerates hydration procession, reducing initial and final setting times by 76% and 42%, respectively, while increasing viscosity by 50% for improved structural stability. At 2% SA, 1-day and 7-day compressive strengths rose from 3.7 MPa to 8.4 MPa and from 15.1 MPa to 18.5 MPa, respectively, representing gains of 127% and 22.5%, which were facilitated by accelerated GGBFS dissolution and needle-like AFt formation, which densifies the crystal-gel network microstructure.