Cationic kraft lignin (CKL) macromolecules were produced via polymerizing kraft lignin (KL) with [2-(acryloyloxy)ethyl]trimethylammonium chloride (ATAC) or [2-(methacryloyloxy)ethyl]trimethylammonium methyl sulfate (METAM). Despite slightly different charge densities (2.3-2.5 mmol/g) of CKL, lignin-METAM (KL-METAM) had a significantly larger molecular weight and radius of gyration. A correlation was observed between the structure of CKLs and their impacts on the surface hydrophilicity of kaolin particles. In interacting with kaolin particles, KL-METAM generated larger and stronger flocs with looser structures than did KL-ATAC. Compared to ATAC, METAM had one additional methyl substituent on its structure, which provided fundamental evidence on how a small group (i.e., a methyl group) on the structure of a cationic monomer can have a substantial influence on its polymerization with lignin and subsequently on the efficiency of the induced macromolecule as a flocculant in a kaolin suspension system.