The organic modification of montmorillonite was successfully achieved using cetyltrimethyl ammonium bromide under facile conditions. The modified montmorillonite was subsequently used for the fabrication of montmorillonite-induced nanopore-rich cement paste (MNCP), and the shrinkage behavior and fundamental performance of MNCP were also investigated. The results indicate that alkali cations on a montmorillonite layer surface were exchanged by using CTAB under 80 °C, successfully achieving the organic modification of montmorillonite. As a pore-forming agent, the modified montmorillonite caused a reduction in shrinkage: the 28-day autogenous shrinkage at a design density of 400 kg/m3 and 800 kg/m3 was reduced to 2.05 mm/m and 0.24 mm/m, and the highest reduction percentages during the 28-day drying shrinkage were 68.1% and 62.2%, respectively. The enlarged interlamellar pores and hydrophobic effects caused by the organic modification of montmorillonite aided this process. Organic-modified montmorillonite had a minor influence on dry density and thermal conductivity and could contribute to an enhancement of strength in MNCP.