The mechanism by which the anionic polymers interact with platelets of 2:1 clay minerals is not fully understood. The objective of the present study was to evaluate the effect of the electric field associated with the basal and edge surfaces of the clay minerals on the adsorption of anionic polymers. Two negatively charged polymers, PAM90 and ACC86, of the same molecular weight (2×105 g mol−1) but with different degrees of hydrolysis (90 and 20%, respectively), were used. The effect of pH (6, 10), NaCl concentration (0, 10 mmolC L −1) and clay particle size on PAM90 adsorption by pyrophyllite and the effect of NaCl concentration on the adsorption of these polymers by Na-montmorillonite in aqueous suspensions were studied. Adsorption of PAM90 on pyrophyllite was greater at pH 6 than at pH 10 and greater in 10 mmol L−1 NaCl than in distilled water. Adsorption of PAM90 on pyrophyllite increased with decreasing particle size. On pyrophyllite the high-charge-density PAM90 was adsorbed to a greater extent than the low-charge-density ACC86; by contrast, ACC86 adsorption was greater than that of PAM90 on Na-montmorillonite. These results were attributed to the repulsive forces which develop between the negatively charged extended-chain polymer and the extended negative electric field associated with the basal surfaces, around the Na-montmorillonite platelets. The results may suggest that the edge surfaces play a major role in PAM adsorption.