This article focuses on the calculation of transport parameters (number density of ions and time travel of ions between sites, mobility, diffusion coefficient, and number of transitions per unit time) of the lithium perchlorate (LiClO4)-doped poly(vinyl alcohol)/chitosan (PVA/CS) composites using Rice and Roth model. The thermal study reveals a decrease in glass transition temperature for LiClO4-doped PVA/CS composites. The highest ionic conductivity of 3 × 10−6S cm−1at room temperature is observed for the 20 wt% LiClO4-containing composite. The temperature-dependent conductivity follows Arrhenius relation and lowest activation energy of 0.153 eV is observed for highest conducting sample. The mechanical properties such as Young’s modulus, stiffness, and tensile strength decreases and its percentage elongation at break increases with increase in LiClO4-doping level in PVA/CS polymer matrix. The scanning electron microscopic images exhibit smooth and homogeneous surface of PVA/CS composite.