Abstract The rheological behavior in the molten state and solution of hyperbranched polyol polyesters (HBPs) obtained by one step (HBP4, HBP5), step by step (HBP4P, HBP5P), and combination of both (HBP1‐4, HBP1‐5) was studied. Under conditions of dynamic oscillatory shear, all HBPs presented a shear‐thinning behavior and under steady shear they showed a Newtonian behavior. Also, the steady shear viscosities decreased with increasing temperature. The behavior of HBPs was mainly viscous, except for the HBP4P that showed higher storage modulus and reduction of complex viscosity when increasing the angular frequency. The HBPs presented higher complex viscosity than steady shear and they did not follow the Cox‐Merz rule. The HBPs in solution presented a plateau region at shear rate lower than 40 s −1 but a shear‐thickening behavior at shear rate higher than 40 s −1 . The viscosities of HBPs in solution (in the plateau region) and molten state increase in the following order: HBP5P > HBP1‐5 > HBP4P > HBP1‐4 > HBP4 > HBP5. These results are not in agreement with the values of the number average molar mass obtained by vapor pressure osmometry due to different interaction between HBPs molecules. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011