Five sodium lignosulfonate (SL) fractions with narrow molecular weight distribution and known salt content were used as the polyanion to build up layer-by-layer self-assembly multilayers with poly(diallyldimethylammonium chloride) (PDAC) as polycation. It is interesting to find that the salt-free SL is hardly adsorbed on the PDAC surface, but the SL in salt-added solutions can be self-assembled well with PDAC to form SL/PDAC multilayers. When the five SL fractions dissolved in saline solutions are adsorbed on the PDAC surface by a self-assembly technique, SL with higher M(w) shows a higher adsorption amount than does SL with lower M(w). The driving forces of self-assembly of SL and PDAC are discussed based on the solution behaviors and adsorption characteristics of SL in salt-free and salt-added aqueous solutions. A possible self-assembled mechanism of SL and PDAC is electrostatic or cation-π interactions, but the SL cannot be adsorbed onto the PDAC surface without a hydrophobic interaction. With the addition of enough salt, the Coulomb interaction of SL becomes negligible, but the adsorption amount increases, indicating that the electrostatic interaction is not the main driving force of SL/PDAC self-assembly. For adsorption of SL in saline solution onto the PDAC surface, the cation-π interaction is the main driving force, and the hydrophobic interaction plays an important role in the adsorbed amount.