This study explores the innovative potential of native lignin as a sustainable biopolyol for synthesizing polyurethane aerogels with variable microstructures, significant specific surface areas, and high mechanical stability. Three types of lignin—Organosolv, Aquasolv, and Soda lignin—were evaluated based on structural characteristics, Klason lignin content, and particle size, with Organosolv lignin being identified as the optimal candidate. The microstructure of lignin polyurethane samples was adjustable by solvent choice: Gelation in DMSO and pyridine, with high affinity to lignin, resulted in dense materials with low specific surface areas, while the use of the low-affinity solvent e.g acetone led to aggregated, macroporous materials due to microphase separation. Microstructural control was achieved by use of DMSO/acetone and pyridine/acetone solvent mixtures, which balanced gelation and phase separation to produce fine, homogeneous, mesoporous materials. Specifically, a 75% DMSO/acetone mixture yielded mechanically stable lignin polyurethane aerogels with a low envelope density of 0.49 g cm−3 and a specific surface area of ~300 m2 g−1. This study demonstrates a versatile approach to tailoring lignin polyurethane aerogels with adjustable textural and mechanical properties by simple adjustment of the solvent composition, highlighting the critical role of solvent–lignin interactions during gelation and offering a pathway to sustainable, high-performance materials.