Organic/Inorganic composite were used as a protective layer of lithium metal electrode for effective suppression of lithium dendrite. PVDF-HFP is a highly flexible polymer that act as a matrix of inorganic materials while TiO₂ nanoparticle improves the mechanical strength and ion conductivity of the protective layer. The as-synthesized protective composite membrane exhibited good dispersion of TiO₂ in the PVDF-HFP matrix by SEM, AFM and XRD analyses. Furthermore, the electrochemical analysis showed that the organic-inorganic composite retained high coulombic efficiency of 80% and low over-potential, less than 20 mV until the 100th cycles due to the improved mechanical properties and ion conductivity in comparison to the control sample (Untreated and PVDF-HFP polymer/Cu).