Lignin, a biopolymer obtained from agricultural/forestry residues or paper pulping wastewater, is rich in aromatic structure, which is central to its adoption as a candidate to natural antioxidants. Through insight into its structural features from biomass, different functional groups would influence lignin antioxidant activity, wherein phenolic content is the most important factor, hence massive studies have focused on its improvement via different pretreatments and post-processing methods. Besides, lignin nanoparticles and chemical modifications are also efficient methods to improve antioxidant activity via increasing free content and decreasing bond dissociation enthalpy of phenolic hydroxyl. Lignin samples exhibit comparable radicals scavenging ability to commercial ones, showing their potential as renewable alternatives of synthesized antioxidants. Besides, their applications have also been discussed, which demonstrates lignin potential as an inexpensive antioxidant additive and consequent improvements on multiple functionalities. This review is dedicated to summarize lignin antioxidants extracted from biomass resources, methods to improve their antioxidant activity and their applications, which is beneficial for realizing lignin valorization.