The efficient valorization of lignin could dictate the success of the 2^nd generation biorefinery. Lignin, accounting for on average a third of the lignocellulosic biomass, is the most promising candidate for sustainable production of value‐added phenolics. However, the structural alteration induced during lignin isolation is often depleting its potential for value‐added chemicals. Recently, catalytic reductive depolymerization of lignin has appeared to be a promising and effective method for its valorization to obtain phenolic monomers. The present study systematically summarizes the far‐reaching and state‐of‐the‐art lignin valorization strategies during different stages, including conventional catalytic depolymerization of technical lignin, emerging reductive catalytic fractionation of protolignin, stabilization strategies to inhibit the undesired condensation reactions, and further catalytic upgrading of lignin‐derived monomers. Finally, the potential challenges for the future researches on the efficient valorization of lignin and possible solutions are proposed.

AlCl₃·6H₂O in a biphasic medium of water/tetrahydrofuran (THF) is effective for the synthesis of 5-hydroxymethylfurfural (HMF) from glucose-based carbohydrates. For glucose, an HMF yield of 61% was achieved in 10 min at 160 °C under microwave heating. The reaction time profile revealed the intermediacy of fructose en route to HMF with a dehydration rate constant that is approximately 4 times that of glucose isomerization to fructose. Addition of NaCl did not increase HMF yields significantly but it diminished lactic acid formation. Disaccharides (maltose and cellobiose) and starch gave good yields of HMF. However, cellulose required a higher temperature (180 °C) and longer reaction time (30 min) to give a modest yield of 37%. Several lignocellulosic biomass variants (corn stover, pine wood, grass, and poplar) were investigated with the AlCl₃·6H₂O biphasic system. The yields of HMF were modest (20–35%) but high concurrent yields of furfural were observed (51–66%). The described AlCl₃·6H₂O–NaCl–H₂O/THF biphasic medium has potential because it is economic, nontoxic, and it exhibits fast kinetics (10 min) under microwave heating.