Lithium-sulfur (Li-S) batteries boast a specific capacity five times greater than current Li-intercalation systems. Still, practical implementation faces challenges tied to liquid electrolytes, i.e., lithium metal dendrites formation, polysulfide redox-shuttle, and flammability [1]. Thus, we focus on developing biodegradable gel polymer electrolytes to overcome these issues, fostering eco-friendly, safer, and more effective energy storage solutions. Polycaprolactone (PCL) emerges as a promising GPE candidate due to its biodegradable nature and broad stability range (~5V vs Li0/Li+). Our current study investigates the influence of solvent selection, explicitly focusing on donor and acceptor numbers, in formulating gel polymer electrolytes for Lithium-Sulfur batteries. Leveraging operando Raman and in-situ UV-Vis spectroscopy, our research provides real-time insights into the dynamic interactions within the gel during battery operation, shedding light on the evolving electrochemical processes. Moreover, by systematically analyzing the impact of solvent properties on gel characteristics, we reveal a nuanced relationship, emphasizing the importance of tailored solvent selection for optimizing gel performance. Operando Raman spectroscopy enables the observation of bond formations and structural changes in the gel, while in-situ UV-Vis spectroscopy tracks the behavior of polysulfides, facilitating the identification of specific interactions and offering a comprehensive understanding of the gel's role in mitigating polysulfide shuttling. This work aims to advance our fundamental knowledge of gel polymer electrolytes and provide a pathway for optimizing battery performance and mitigating degradation mechanisms. Notably, our study introduces a novel dimension by employing a custom-built UV-Vis setup, enhancing the versatility and applicability of these spectroscopic techniques in probing the intricate interactions within gel polymer electrolytes.Reference1-Pervez, S. A.; Vinayan, B. P.; Cambaz, M. A.; Melinte, G.; Diemant, T.; Braun, T.; Karkera, G.; Behm, R. J.; Fichtner, M., Electrochemical and compositional characterization of solid interphase layers in an interface-modified solid-state Li–sulfur battery. Journal of Materials Chemistry A2020, 8 (32), 16451-16462.