AbstractBio‐based industries (pulp and paper and biorefineries) produce > 50 Mt/yr of lignin that results from fractionation of lignocellulosic biomass. Lignin is world's second biopolymer and a major potential source for production of performance materials and aromatic chemicals. Lignin valorization is a key‐issue for enhanced profitability of sustainable bio‐based industries. Despite a myriad of potential applications for lignin and decades of research, its heterogeneity and recalcitrance still preclude commercial value‐added applications. Most lignin is utilized for heat and power. Unconventional solutions are needed to better exploit lignin's potential. Organosolv lignins are especially suitable as feedstock for high‐value chemicals. AtECN, a lignin biorefinery approach (LIBRA) has been developed, involving a dedicated lignin pyrolysis protocol that is robust, continuous, and capable of processing different lignins. Typical product yields are 20% gas, 35% char, and 45% oil. The oil contains approximately 45% oligomeric phenolic substances, 23% monomeric phenols, and 33% water. The future perspective is scale‐up of the process to produce larger lignin pyrolysis oil samples for separation, purification, and industrial application tests. Presently, small lignin pyrolysis oil samples are investigated as feedstock for extracting high‐value chemicals, as a substitute for phenol in several applications, and as a feedstock for hydrotreating. The biochar is tested as growth enhancer and as substitute for carbon‐black in rubber. Regarding the large lignin side streams from (future) bio‐based industries, theLIBRApyrolysis technology has ample potential to increase the profitability of lignocellulosic biorefineries provided that for both the liquid product and the solid char value‐added applications are developed. © 2014 Society of Chemical Industry and John Wiley & Sons, Ltd