Cement grout is traditionally used for treating water leakage distress in tunnels. However, traditional cement grout has the disadvantages of a poor anti-seepage performance, long setting time, and slow strength gain. To this end, a high-performance cement-based capillary crystalline waterproofing (CCCW) grouting material was synthesized using cement, capillary crystalline material, and several admixtures. The influences of the material proportions on the viscosity, bleeding rate, and setting time of the fresh grout, as well as the permeability coefficient of the grouted aggregate and the unconfined compression strength of the hardened grout material, were systematically studied. The mineralogy and microstructure of the CCCW grouting material were examined using X-ray diffraction, industrial computed tomography, and scanning electron microscopy. The results indicated that the capillary crystalline material PNC803 was not suitable for mixing with bentonite, sodium chloride, and triethanolamine in cementitious slurries, but it can produce excellent synergistic effects with sulfate, calcium chloride, and triisopropanolamine. An analysis of the microstructure of the CCCW grouting material showed that the PNC803 and additives can promote the hydration of cement, which yields more hydration products, sealing water passage and filling micro voids and therefore leading to enhanced waterproofing and strengthening effects. These research results could improve the applicability of CCCW material in tunnel engineering.