This article demonstrates the direct intercalation of an epoxy polymer in the interlayer of Na+-montmorillonite (MMT) by a step type of polymerization in an aqueous emulsion media. The synthesis and the results of structural and thermal characterizations for this hybrid composite are described. Equimolar quantities of bisphenol A and an epoxy prepolymer (n = 0.2) in an emulsion media were polymerized in the presence of Na+-MMT. X-ray diffraction (XRD) data obtained from the acetone-extracted products show that the basal spacing of the MMT is expanded from 0.96 to 1.64 nm. Thermal characterization for the postcured products by TGA and DSC gave evidence of enhanced thermal stabilities. SEM examination of the uncured products revealed that a disordered phase begins to appear with increasing polymer loading. However, the XRD prose supported that an overwhelming fraction of the nanocomposite contains intercalated clay. Also, the possibility of intercalation by the emulsion technique is proposed on the basis of the swelling characteristics of MMT in aqueous media and the sizes of micelles containing a monomer.