Lithium ion batteries are an important area of research. The use of biodegradable polymers in batteries has gained importance recently. To have high efficiency, the lithium ions available for conductivity should be high. Understanding the effect of LiClO 4 upon the assembly of polymers could be useful. For that, chitosan films with LiClO 4 were chosen. We have used various techniques that include X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), small-angle neutron scattering (SANS), and broadband dielectric spectrometer (BDS) for our study. Our investigations show that LiClO 4 induce the assembly of chitosan as star-like nanostructures. The assembly of the polymer chains could trap the ions and affect the conductivity. Our investigations show that LiClO 4 encapsulates the chitosan and forms globule-like structures. This research could help us in our understanding of using biomolecules for lithium ion batteries.