This paper presents the investigation on physicochemical properties and ionic conductivity of LiClO4-doped poly(vinyl alcohol) (PVA)/modified cellulose composites. The percolative behaviour of LiClO4 with dc conductivity (𝜎dc) for different LiClO4 weight fractions (p) related to transport dimensionality was also focused. The highest ionic conductivity of 9.79 × 10–6 S cm–1 was observed for 20 wt% LiClO4 doping level at room temperature. The activation energies (𝐸g) were estimated using temperature-dependent conductivity, which follows the Arrhenius and Vogel–Tammann–Fulcher (VTF) relation. The dynamic fragility (𝑓) and activation energy (𝐸g) vs. 𝑇g of polymer composites using equivalence of the both Williams–Landel–Ferry (WLF) and VTF equations were also correlated. Transport properties such as travel time of ions between sites (𝜏o), mobility (𝜇), diffusion coefficient (𝐷) and number of transitions per unit time 𝑃(𝐸) for normal cationic (Li+) hopping process of LiClO4-doped PVA/mCellulose composites have been investigated using the Rice and Roth model.