The synthesis, diffraction patterns, thermal stability, and ionic conductivity properties of methacrylate‐type polymers are analyzed here to assess their feasibility as polymer electrolytes. From the parent polymer, poly (N,N‐dimethylaminoethylmethacrylate), herein labeled PDMAEMA, a protonated derivative was used to prepare polymer/Montmorillonite nanocomposites with various clay contents (1, 3, and 5 wt %). AC spectroscopy provided the ionic conductivity data for the polymers and clay–polymer nanocomposites. Evidences of nanocomposite formation are shown using transmission electron microscopy and wide‐angle X‐ray diffraction. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011