Nanochitin has been incorporated in a poly (ethylene oxide) (PEO)-LiPF6 matrix for the first time. The incorporation of chitin whiskers significantly improves the ionic conductivity, thermal stability, mechanical integrity along with the interfacial properties. The prepared membrane is also tested in a LiFePO4/C–Li cell and the galvanostatic cycling behaviour is analysed at 70 °C showing an improved specific capacity and outstanding cycling stability. The obtained results and the use of such environment friendly component would make these hybrid organic, nanochitin-based composite polymer electrolyte systems a strong contender in the field of flexible and green lithium-based power sources.