The assembly of dissolved technical lignins in aqueous and organic medium has been studied at the solid-liquid interface. Adsorption of alkali lignin onto gold coated crystals treated with a cationic polymer was determined using a quartz crystal microbalance with dissipation monitoring. Complete coverage of the cationic surface with alkali lignin occurred at low solution concentration, revealing a high affinity coefficient under both alkali and neutral conditions. With additional adsorption studies from organosolv lignin in organic solvent and spectroscopic analysis of mixtures of cationic polymer and alkali lignin, a noncovalent interaction between lignin's aromatic rings and the cation of the quaternary ammonium group was shown to exist. The work underscores how polyphenolic biopolymers can strongly interact with cations through noncovalent interactions to control molecular architecture.