Since filling slurry is a cement-based material, viscosity-enhancing admixture exerts a significant effect on its rheological performance and mechanical properties. Viscosity-enhancing admixture can improve pipeline transportation performance and reduce pipeline wear during the filling process of a kilometer-deep mine by changing the plastic viscosity and yield stress of high-concentration filling slurries. In order to reveal the influence mechanism of viscosity-enhancing admixture on rheological performance in slurry, the influence of viscosity-enhancing admixture on the rheological performance of slurry is explored by adjusting viscosity-enhancing admixture dosage and conducting bleeding test, liquidity test, and rheological performance test. The extended DLVO theory is employed to analyze the mechanism of HPMC on the stability of filling slurry. The results show that compared with ordinary slurry, after adding HPMC and XG, the particles of filling slurry are prone to link to form a mesh structure. Besides, the increasing frictional force between particles results in a significant decrease in the bleeding rate and liquidity of the slurry. Such an effect becomes more obvious with the increase of viscosity-enhancing admixture dosage. Meanwhile, the overall effect of HPMC molecules is better than that of XG molecules since HPMC can reduce inter-particle repulsion and facilitate particle aggregation. The optimal dosage is about 0.1%, at which time the yield stress of the filling slurry increases from 89.236 to 160.06 Pa, the plastic viscosity increases from 0.296 to 1.063 Pa·s, and the compressive strength increases from 2.58 to 3.59 MPa in 28 days. The study reveals the influence of viscosity-enhancing admixture on the rheological performance of filling slurry and its evolution characteristics, which provides theoretical support for the development of filling resistance and wear reduction technology.