In this study, the poly-vinylidene fluoride (PVDF)/p-benzoquinone (pBQ) gel polymer electrolyte (GPE) is synthesized well with LiTFSI/TEGDME for Li-air battery (LAB) applications. The PVDF/pBQ GPEs are characterized by electrochemical analysis and compared to the PVDF GPE. We confirm that pBQ molecule in PVDF GPE shows redox mediate behavior during charge-discharge process. Employing PVDF/pBQ GPE for LAB leads to an improved cycleability from 2 to over 30. In addition it results in a charge voltage decrease from around 4.2V to around 3.3V. The energy cycle efficiency (ECE) is improved about 15%. The pBQ accelerates to the formation of an amorphous phase on synthesized PVDF GPE matrix by acting inhibitor for polymerization. It leads to ionic conductivity improvement of synthesized GPE from 2.83 mScm−1 to 4.98 mScm−1.