Understanding the structure of hardwoods can permit better valorization of lignin by enabling the optimization of green, high-yield extraction protocols that preserve the structure of wood biopolymers. To that end, a mild protocol was applied for the extraction of lignin from ball-milled birch. This made it possible to understand the differences in the extractability of lignin in each extraction step. The fractions were extensively characterized using 1D and 2D nuclear magnetic resonance spectroscopy, size exclusion chromatography, and pyrolysis-gas chromatography-mass spectrometry. This comprehensive characterization highlighted that lignin populations extracted by warm water, alkali, and ionic liquid/ethanol diverged in structural features including subunit composition, interunit linkage content, and the abundance of oxidized moieties. Moreover, ether- and ester-type lignin-carbohydrate complexes were identified in the different extracts. Irrespective of whether natively present in the wood or artificially formed during extraction, these complexes play an important role in the extractability of lignin from ball-milled hardwood. Our results contribute to the further improvement of lignin extraction strategies, for both understanding lignin as present in the lignocellulosic matrix and for dedicated lignin valorization efforts.