The low-permeability argillaceous rock mass is an unfavorable geological body commonly found in the construction process of underground engineering conditions such as roadways and tunnels. Due to the compact structure and low permeability of the rock mass, grouting with conventional materials cannot effectively seal the micro-cracks of the rock mass. Based on the low efficiency of high-pressure grouting of nano-silica sol, this paper preliminarily explores the regularities and mechanism of grouting and pore sealing of low-permeability rock mass under the action of silica sol imbibition from the aspects of gelling properties of silica sol, core pore structure, imbibition law, and pore sealing characteristics. The results show the following: (1) The increase in particle size during the gel process reduced the injectability and wettability of the silica sol. The imbibition properties of silica sol were time-varying, and the deterioration inflection points of injectability and wettability appeared at 10 h and 9 h, respectively. (2) Catalyst, temperature, gel process, and rock mass permeability will affect the law of core imbibition, and the injectability and capillary force of the grouting material and rock mass will jointly affect the imbibition process of silica sol. (3) Silica sol imbibition changed the pore size distribution of the core, the pore volume above 50 nm decreased, and the pore volume below 50 nm increased. Silica sol has multiple effects such as filling, adsorption, and percolation in the imbibition process of the micro-pores of rock mass, and the adsorption and percolation of silica are related to the nano micro-pores.