Macromonomers (MMs) were obtained with different proportions of dimethylolpropionic acid (DMPA) and tall oil fatty acid (TOFA). The MMs were characterized by their acid value (AV), their hydroxyl value (OHV), IR spectroscopy, NMR, electrospray ionization–mass spectrometry, UV spectroscopy, rheological, differential scanning calorimetry, thermogravimetric analysis, gloss, flexibility, and adherence analyses. The presence of hydroxyl and ester groups and double bonds were confirmed by IR and NMR analyses. IR analysis showed that the intensity of the OH groups decreased with the addition of TOFA. In all cases, the AVs of the MMs were lower than those of DMPA and TOFA. By electrospray ionization–mass spectrometry, the formation of the DMPA homopolymers and structures with molecular weights higher than that of DMPA were observed. All of the MMs were amorphous. The viscosity of the MMs decreased with the addition of TOFA. The gloss values of the MMs at 85° were higher than 100, and the flexibility was good. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42029.