The sodium montmorillonite was organic modified with three kinds of quaternary ammonium salts containing 1 to 3 octyl chains, and then the organic montmorillonite was studied by FT-IR, XRD, and TG characterization as well as Monte Carlo simulations, to explore the influence of the number of octyl chains and the loading of intercalated cations on the basal spacing (d001) of the modified montmorillonite complexes. According to the distribution of intercalated quaternary ammonium cations and the energy change of the montmorillonite complexes, a reasonable explanation was given for the enlargement of the interlayer space. The results of experimental characterization and Monte Carlo simulations show that all the three intercalation agents can enlarge the interlayer space of montmorillonite complexes. The more the number of octyl chains in the salt, the more significant expanding effect on the interlayer space. The three intercalation cations exhibited a distribution arranged from mono-layered to multi-layered structure as the loading of intercalated cations increases.