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Hydroxypropyl methylcellulose (HPMC) is blended with methyl gallate (MG) encapsulated with poly(ethylene glycol) (PEG) and then mixed with a liquid electrolyte to prepare a polymer gel electrolyte. The structural and physical properties of prepared polymer gels are analyzed by various analytical instruments. The MG‐PEG‐HPMC hybrid is found to be able for entrapping a large amount of liquid electrolyte and is used to fabricate dye‐sensitized solar cells (DSSCs). This polymer gel electrolyte shows high ionic conductivity (5.43 × 10−4 S cm−1) and good triiodide diffusion coefficient (2.25 × 10−6 cm2 s−1). The resulting DSSCs show an efficiency of 6.96% at a light intensity of 85 mW cm−2. The long‐term stability test reveals that the fabricated DSSCs will be stable even after 500 h. The benefits of incorporating a gel electrolyte into DSSCs are highlighted along with factors affecting the stability of these devices. The use of these bio‐based materials has the potential to make a significant contribution to the widespread exploitation of stable, efficient, and low‐cost dye‐sensitive solar cells.

Substantially to increase the efficiency of dye‐sensitized solar cells (DSSCs), it has been fabricated with the polymer gel electrolytes (PGEs) by replacing the liquid electrolytes (LEs). Poly (ε‐caprolactone) (PCL) has been synthesized as a crystalline solid biopolymer of about 74% yield using different 6‐membered ring phenolate Al complexes. As prepared PCL was blended with LE used in dye‐sensitized solar cells (DSSCs) to prepare high polydispersity index (PDI) PGE. The prepared PGE shows cross‐linking between carboxyl and hydroxyl groups and interacts with iodide ions to form a chelate complex structure. The PGE was well‐characterized using various analytical tools to demonstrate its structural and surface morphology. The fabricated DSSCs using PGE showed high ionic conductivity (7.76 × 10−4 S cm−1), good tri‐iodide diffusion (2.052 × 10−6 Cm2 S−1), and a highly stable incident photon‐to‐current conversion efficiency (PCE; 5.92%) under solar light illumination (85 mW cm−2). Besides found PGE has improved long‐term stability up to 15 days, and these results proved that the prepared PGE is superior compared to other reported PGEs.