Lignin is one of the most complex biopolymers and is characterized by combination of monomers to form a variety of inter-monomer linkages, which successively build up the racemic polymer. The prevailing theory of lignin formation suggests that monomers are enzymatically oxidized into resonance-stabilized radicals that subsequently couple through radical–radical reactions to generate intermediates that are then stabilized via post-coupling reactions. However, this standard model for lignin formation is challenged by certain lignin structures that cannot be easily explained by this theory. One such structure characterized by a side chain carbon (α or β-position) linked to an aromatic C6 is the focal point of this minireview. The evidence supporting the presence of this structure in softwood lignin is scrutinized, leading to the conclusion that this type of structure is most likely formed during the lignification process. Possible mechanisms for its formation are discussed.