ABSTRACT In this study the modification of a hyperbranched polyester polyol of second generation (HBP2G) with polylactic acid (PLA) was carried out. The proportions employed of PLA were: 10 (HBP2G90), 25 (HBP2G75), 40 (HBP2G60), and 55 wt % (HBP2G45). The materials obtained were characterized by acid value, hydroxyl value, infrared, nuclear magnetic resonance (NMR), chromatography exclusion size (SEC), dynamic light scattering, thermogravimetric, differential scanning calorimetry, and rheology analyses. The analyses of the acid values and hydroxyl values showed that the reaction between HBP2G and PLA occurred. The greater modification degree was 92.00%. The NMR spectrum shows that evidently the PLA was grafted onto the HBP2G. The SEC analysis revealed that all samples presented values ​​of average molecular weight ( M n ) and weight average molecular weight ( M w ) higher than the HBP2G. The thermal stability of the materials increased with respect to HBP2G and it was independent of the modification degree. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132 , 41589.