Polymer nanocomposites were prepared from poly(oxyethylene) PEO as the matrix and high aspect ratio cellulose whiskers as the reinforcing phase. Nanocomposite films were obtained either by extrusion or by casting/evaporation process. Resulting films were characterized using microscopies, differential scanning calorimetry, thermogravimetry and mechanical and rheological analyses. A thermal stabilization of the modulus of the cast/evaporated nanocomposite films for temperatures higher than the PEO melting temperature was reported. This behavior was ascribed to the formation of a rigid cellulosic network within the matrix. The rheological characterization showed that nanocomposite films have the typical behavior of solid materials. For extruded films, the reinforcing effect of whiskers is dramatically reduced, suggesting the absence of a strong mechanical network or at least, the presence of a weak whiskers percolating network. Rheological, mechanical and microscopy studies were involved in order to explain this behavior.