Lignin, a vital structural component of lignocellulosic biomass, holds immense potential for valorization despite traditionally being regarded as a low-value residue. This chapter delves into the use of γ-valerolactone (GVL), an innovative green solvent, for the efficient extraction of lignin from various biomass sources. GVL offers numerous advantages, including high selectivity, chemical stability, and low toxicity, positioning it as a sustainable alternative to conventional solvents. The chapter thoroughly examines the solubility parameters, extraction processes, and characteristics of lignin obtained using GVL. It highlights optimal conditions for lignin recovery, emphasizing the importance of solvent composition, temperature, and catalyst presence. The discussion extends to the impact of GVL-extracted lignin on biorefinery applications, particularly in improving cellulose accessibility for biofuel production. The findings underscore GVL’s potential in advancing sustainable biomass conversion technologies. Future research directions focus on optimizing GVL-based processes and exploring novel applications to fully harness its potential in lignin valorization and integrated biorefinery systems.