Composite polymer electrolyte (CPE) films with high room temperature ionic conductivity are urgently needed for the practical application of high-safety solid-state batteries (SSBs). Here, a flexible polymer-polymer CPE thin film reinforced by a three-dimensional (3D) bacterial cellulose (BC) framework derived from natural BC hydrogel was prepared via the in situ photo-polymerization method. The BC film was utilized as the supporting matrix to ensure high flexibility and mechanical strength. The BC-CPE attained a high room temperature ionic conductivity of 1.3 × 10 -4 S cm -1 . The Li∣BC-CPE∣Li symmetric cell manifested stable cycles of more than 1200 h. The LCO∣BC-CPE∣Li full cell attained an initial discharge specific capacity of 128.7 mAh g -1 with 82.6% discharge capacity retention after 150 cycles at 0.2 C under room temperature. The proposed polymer-polymer CPE configuration represents a promising route for manufacturing environmental SSBs, especially since cellulose biomaterials are abundant in nature.