A series of poly(ethylene oxide) (PEO)/organoclay nanocomposites have been prepared via a solvent casting method. Using three different organoclays modified with the alkylammonium salts, the effect of surfactants on organoclay surfaces in polymer/organoclay nanocomposites was investigated by focusing on two major aspects: internal structure analysis and rheological measurement of the nanocomposites. The d spacings of both the pure PEO and intercalated organoclay were examined via X-ray diffraction analysis, and the microstructure of these nanocomposites was examined by transmission electron microscopy. Rheological properties of these nano composites exhibited different behavior with different modifier concentrations and surfactant sizes (chain lengths). To analyze the non-Newtonian flow behavior, we fitted shear viscosity data via the Carreau model, showing that steady shear viscosity and power-law behavior increase with organoclay content. Hysteresis phenomenon was also enhanced with organoclay content, and the increase in the storage/loss moduli and interactions among organoclay platelets were observed with organoclay content. The enhanced thermal stability of the nanocomposites by organoclay was also observed.