Adsorption of polymers from an aqueous solution onto clay minerals is of great interest to many applications such as water purification and soil conditioning. Molecular dynamics simulations were performed to study the adsorption of anionic polyacrylamide (APAM) on anionic montmorillonite, in an aqueous solution containing monovalent or divalent salts. Compared with monovalent salts (NaCl), the enhancement of APAM adsorption brought by divalent salts (CaCl2) was significant, which could not be explained by the Poisson-Boltzmann theory alone. Each solvated Ca2+ was coordinated by 4-6 water oxygens in its first coordination shell. One to two of these water molecules were displaced when APAM formed a complex with Ca2+. Ca2+ ions in the adsorbed Ca2+-APAM complexes did not serve as bridges sandwiched between APAM and Mt; instead, the complexes carried a residual positive charge and were subsequently attracted to montmorillonite. The number of adsorbed Ca2+-APAM complexes changed with salinity in a nonmonotonic in a nonmonotonic due to the manner, modulation of apparent charges of montmorillonite and APAM by Ca2+. Increasing adsorption of Ca2+-APAM complexes also promoted APAM adsorption through direct hydrogen bonding with montmorillonite. The findings provided new molecular insights into the long-standing debates on the role of divalent ions in promoting polymer adsorption on like-charged solid surfaces.