Nanocomposite polymer electrolytes composed of high molecular weight poly(oxyethylene) PEO as a matrix, LiTFSI as lithium salt and ramie, cotton and sisal whiskers with high aspect ratio and sisal microfibrils (MF), as reinforcing phase were prepared by casting-evaporation. The morphology of the composite electrolytes was investigated by scanning electron microscopy and their thermal behavior (characteristic temperatures, degradation temperature) were investigated by thermogravimetric analysis and differential scanning calorimetry. Nanocomposite electrolytes based on PEO reinforced by whiskers and MF sisal exhibited very high mechanical performance with a storage modulus of 160 MPa at high temperature. A weak decrease of the ionic conductivity was observed with the incorporation of 6 wt% of whiskers. The addition of microfibrils involved a larger decrease of the conductivity. This difference may be associated to the more restricted PEO mobility due to the addition of entangled nanofibers.