To study the rheological properties of grouting materials, the effects of sand-binder ratio, water-binder ratio, and rest time on the rheological model and parameters were studied through rheological tests. Through the cryo-scanning electron microscopy test to observe the structural build-up process of microstructures with rest time, the particle size test to measure the size distribution variation of flocculated structures over rest time, and the low-field nuclear magnetic resonance test to measure the change of water content in the slurry, the evolution mechanism of yield stress was studied. The results showed that the rheological model was consistent with Herschel–Bulkley model (H–B model). The yield stress increased with time. The growth of network flocculated structures and the decrease in the lubrication effect of water caused an increase in the aggregate particles–cement paste interaction stress. Therefore, the yield stress of the grouting materials increased over time. Considering the combined influences of the flocculation effect, hydration reaction, and the aggregate particles–cement paste interaction, a new evolution model was proposed to better describe the evolution law of yield stress with time. The results could provide a basis for the study on flow diffusion of grouting materials and an in-depth understanding of the time-dependent rheological properties of cement-based materials containing aggregate particles.