AbstractSelf-assembled multilayers were fabricated from lignosulfonate (LS) and poly(diallyldimethylammonium chloride) (PDAC), and the adsorption and desorption behaviors of LS on the LS/PDAC multilayers under different pH conditions were intensively investigated. Results showed that the adsorption and desorption behaviors were controlled by electrostatic attraction, hydrophobic interaction, and changes in the microstructure, which depended on solution pH. Lignosulfonates exist as colloids in solutions at low pH because of a hydrophobic interactions, and the LS colloids adsorbed on the PDAC layer because of electrostatic attraction. LS colloids started to disassociate at pH 3.5, resulting in an abrupt rise of the adsorption rate, a sharp decrease of the adsorbed amount, and a steep reduction in the surface roughness. Desorption behaviors of LS multilayers were related to the pH values of both LS dipping solution for self-assembly and the immersing solution for post-preparation treatment. Desorption of LS could be induced by a weakening of electrostatic attraction or hydrophobic interaction. A significant desorption occurred only when LS colloids dissociated in the multilayers. LS colloids were harder to dissociate in the multilayers than in the solutions because of electrostatic attraction between LS and PDAC.