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The process of forming the unique organic/inorganic network structure of nanocomposite hydrogels (NC gels) was studied through changes in viscosity, optical transparency, X-ray diffraction, and mechanical properties. It was concluded that, during the preparation of the initial reaction solutions, a specific solution structure was formed from monomer (NIPA) and clay, where NIPA prevents gel formation of clay itself, and initiator (KPS) is located near the clay surface through ionic interactions. In subsequent in-situ free-radical polymerization, it was observed that the viscosity increased markedly during NC gel syntheses and in a manner similar to that in OR gel syntheses. Also, NC gels with different polymer contents exhibit characteristic two-step changes in the stress−strain curves, which correspond to the primary network formation and subsequent increase of cross-link density. These are because the polymerization proceeds on the clay particles which are relatively immobile, and clay platelets act as effective multifunctional cross-linking agents (plane cross-link). Then, it was proposed that clay−brush particles, consisting of exfoliated clay platelets with numbers of polymer chains grafted to their surfaces, were formed in the very early stage of polymerization, at around 7% of monomer conversion. Novel decreases in transparency were observed corresponding to the formation of clay−brush particles, but transparency recovered on further polymerization. Clay−brush particle formation was confirmed by XRD measurements on dried NC gels prepared using small amounts of monomer. Thus, a mechanism for forming the unique organic/inorganic network structure, including the formation of clay−brush particles in the synthetic pathway, is proposed. Furthermore, it was found that NC gels with excellent mechanical properties and structural homogeneity could not be prepared using other methods such as mixing clay and polymer solutions or by in-situ polymerization in the presence of the other inorganic nanoparticles instead of clay. These results indicate that the formation of organic/inorganic network structures in NC gels is highly specific and only realized by in-situ free-radical polymerization in the presence of clay.