Carbohydrate polymers have broad application prospects, especially in food and cosmetic fields, and rheology is very important for controlling the quality and functions of their final products. Therefore, the steady and transient rheological behaviors of polysaccharides with different chain conformations of triple helix, double helix, and random coils were studied systematically. In our findings, the extraordinary low‐shear thickening phenomena of polysaccharides (lentinan, curdlan, and xanthan) with helix conformation were observed at a certain concentration depending on the stiffness and molecular weight, different from the steady‐shear rheological property of pullulan, which was attributable to the arrangement from order to disorder of stiff chains at the shear rate of < 0.1 s−1. Lentinan, curdlan, and xanthan in solution showed obvious viscoelasticity and thixotropic behavior with significant concentration and stiffness dependence, while the flexible pullulan only exhibited Newtonian viscous fluid even at high concentration of 20%. Stress overshoot for the four polysaccharides occurred after shearing, and the higher stiffness and molecular weight delayed the occurrence of stress overshoot. Obviously, chain conformation plays a key role on controlling the rheology of polysaccharides. This work provides scientific basis for the application of these polysaccharides in food and cosmetics field.