At the present, Portland cement-water glass double solution grouting materials have many problems, such as the instability of gelation time and of products, and poor groundwater-corrosion resistance performance, etc. A way to improve the performances of double solution grouting materials was studied by adding metakaolin into the systems. Based on the rapid gelation performance of Portland cement-water glass and the durability of alkali-activated salic cementitious materials, an ideal structural model of the novel anti-aqueous dispersion and anti-aqueous dissolution grouting material (AAGM) was established. Series of experiments were prepared to verify the Na+ solidification and water-corrosion resistance performance of the metakaolin-water glass double solution grouting materials which combined with cement. The results indicated that the compact structure of AAGM was composed of a dominant ingredient of (Na,Ca)-Si-Al-H zeolite gel and a minor part of C-S-H. Moreover, it was shown that the AAGM had hydrated product of low solubility and compact microstructure tested by Fourier transform infrared spectra (FTIR) and transmission electron microscopy (SEM), which proved the well anti-aqueous dispersion and anti-aqueous dissolution performance.