Tailings from gold mines gradually approach ultra-fine, making mine backfill costs higher and strength lower, which poses a serious threat to the safety of underground personnel and equipment. It is well known that suitable chemical admixtures can enhance the working properties of mortar materials. Therefore, in order to achieve the purpose of reducing the cost of ultra-fine tailings backfill and improving the working performance of ultra-fine tailings filling slurry, this paper provides a study on the effect of sodium silicate and calcium chloride on the properties of ultra-fine tailings cemented backfill materials. The results of experimental studies through rheology, strength, and microstructural tests, etc., showed that the optimal proportioning parameters of cementitious materials are 76.92% blast furnace slag, 19.24% carbide slag, and admixtures of 2.88% sodium silicate and 0.96% calcium chloride. The 3, 7, and 28-day uniaxial compressive strength of the ultra-fine tailings cemented paste backfill with the newly formulated blast furnace slag-based cementitious material increased by 124%, 142%, and 14%, respectively, compared to that of the ultra-fine tailings cemented paste backfill with the P. O42.5 cement. The setting time for ultra-fine tailings cemented backfill slurry is shortened by the addition of admixtures, and the shear stress of the slurry is correlated with the amount of hydration product generation and its formation of flocculating structure. Moreover, the cost of the newly prepared cementitious material is much lower than that of traditional cement, which lays a good foundation for the cemented filling of ultra-fine tailings.