The adsorption of guanidine polymer modified starches on cellulose fibers was investigated along with the systematic studies on various influencing factors including temperature, pH, ionic strength and charge density of the starches. The AFM results revealed the relationship between the adhesion force and adsorption capacity. The adsorption capacity is not necessarily proportional to the adhesion force. The conditions for achieving the maximum adsorption were: temperature, 40°C; pH, 6; C NaCl , 0 mM and charge density, 0.4 meq/g. The corresponding the normalized adhesion force is approximate 1 mN/m. In terms of the surface roughness determined by AFM, it has been proved that adsorbed starches of high charge density tend to form train structure, whereas those of low charge density tend to form tails and loops. Due the comb molecular structure, the adsorption capacity of the novel cationic starch reaches 124.3 mg/g, which is much greater than those reported previously.