In lignin-first biorefining via reductive processes, lignocellulosic materials are deconstructed by the solvent extraction of lignin in the presence of a hydrogenation catalyst. This approach provides a route to the successful extraction and reductive passivation of lignin fragments to produce low molar mass lignin oils together with high-quality pulps. Herein, we present an investigation into the impact of process severity (i.e., cooking temperature) on the reductive processes taking place on the lignin fragments and uniformity of the product mixture. In addition to improving overall delignification yields (up to 87%) and producing low molar mass fragments, higher process temperatures led to the preferential cleavage of hydroxyl groups in monolignol sidechains via hydrodeoxygenation, yielding oils with lower oxygen content. By comparing products from both lignin-first biorefining and organosolv processes at various temperatures, we elucidate key performance differences and outline routes to increased chemical uniformity in lignin streams. Overall, this study outlines clearly the importance of process temperature in the deconstruction of lignocellulose by lignin-first biorefining when producing highly depolymerized lignin products. This study points out a trade-off in the effect of temperature upon delignification and increase in product mixture complexity, which needs to be carefully optimized for the scale-up of lignin-first technologies.