Mineral admixtures (MA), like fly ash (FA), silica fume (SF), and slag (S), are usually added to cement-based materials to improve their compactness and further enhance their mechanical properties, permeability resistance, and durability. In this study, low-field nuclear magnetic resonance (LF-NMR) is adopted to explore the evolution of the early hydration characterization of cement-based materials with MA by testing the transverse relaxation time T2. Meanwhile, the effect of MA on mechanical properties is analyzed by measuring compressive and flexural strength. The results show that, in the early hydration (0–7 days), the T2 distribution shows a trend of gradually moving to a short relaxation time and changes from a double peak to a single main peak. The decrease in T2i (main peak vertex) means that the evaporated water is gradually distributed in smaller pores with more motion constraints. However, the type and content of MA have little effect on T2i. Porosity gradually decreases in the period of early hydration. The addition of MA causes the porosity to decrease, and the order influence is FA > S > SF, i.e., the porosities of cement paste with 0%MA, 10%FA + 10%SF, 10%FA + 10%S, and 20%FA at 7 days are 48%, 44.5%, 40.7%, and 40.2%, respectively. Additionally, the addition of MA to cement-based materials also decreases the early strength, and the influence order is FA > S > SF, i.e., the compression strength values of cement paste with 0%MA, 10%FA + 10%SF, 10%FA + 10%S, and 20%FA at 7 days are 47.8 MPa, 40.1 MPa, 38.6 MPa, and 37 MPa, respectively.