Sodium silicate has been widely used as starting materials of chemical grout owing to its feasibility and short setting time with reasonable strength. Elution of sodium has been pointed out as the main reason of weak durability of homogel prepared with sodium silicate-cement grout. There are well known series of additives for controlling its setting time, fluidity, and compressive strength. We studied the structural change on the sodium silicate with additive of sodium tripolyphosphate (STPP) by 29Si nuclear magnetic resonance spectrum and viscosity. The homogel was prepared by mixing cement/water suspension and diluted sodium silicate/STPP mixtures, and aged in the water. The development of compressive strength and its structural change were observed using a universal test machine, X-ray diffraction, and scanning electron microscope. The additive changed the distribution of Si and rheological property of liquid sodium silicate, which caused more uniform distribution of Ca and Si in the homogel to lead to high initial strength and durability.