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Solvent selection guides are crucial in chemical process design and development. Lignin from lignocellulosic biomass is a potentially attractive feedstock for sustainable chemical feedstocks. One approach would use a solvent to recover lignin prior to the traditional pulping process to make cellulose fibers: lignin value prior to pulping (LVPP). A solvent selection methodology for LVPP is presented herein that may be expanded for any proposed solvent for this process. Four screening categories are elucidated, providing metrics for 30 solvents across multiple molecular functional groups. Through performance, hazards and environment, cost and availability, and process‐economics screens, the initial list of solvents is reduced to two top‐tier candidates, 1,6 hexamethylenediamine and diethanolamine. 1‐Methylpiperazine also emerged as a potential candidate. This solvent‐selection methodology streamlines experimentation and provides promising candidates for LVPP. In addition to creating a tailored solvent selection guide, valuable biomass pretreatment data that may be utilized in different renewable applications are also presented. [ABSTRACT FROM AUTHOR]