Over 14 billion tons of mine tailings are produced throughout the world each year, and this type of waste is generally stored onsite indefinitely. Alkali activation is a promising strategy for the reuse of mine tailings to produce construction materials, converting this waste stream into a value-added product. One major problem with alkali-activated mine tailings is their low durability in water (i.e., low hydrolytic stability). In this article, the influence of a mixed sodium hydroxide/sodium silicate alkali activator on the compressive strength, hydrolytic stability, and microstructure of alkali-activated materials (AAMs) were systematically investigated. XRD, FTIR, NMR, and NAD were used to investigate microstructural changes, and a water immersion test was used to show improvements in hydrolytic stability. For gold mine tailings activated with pure sodium hydroxide, the compressive strength was 15 MPa and a seven-day water immersion test caused a strength loss of 70%. With an addition of 1 M sodium silicate in the activator, the AAMs achieved a compressive strength of over 30 MPa and strength loss of only 45%. This paper proposes a mechanism explaining why the strength and hydrolytic stability of AAMs are dependent on the dosage of soluble silicate. A high dosage of sodium silicate inhibits the depolymerization of the source material, which results in a sample with less amorphous aluminosilicate gel and, therefore, lower hydrolytic stability.