ABSTRACTAzelate polyols of 2000 g mol−1 have been successfully prepared via esterification of renewable azelaic acid with linear diols containing different number of CH2 repeating units. Structure–property correlation of the azelate polyols had been evaluated in thermoplastic polyurethanes (TPUs). TPUs based on azelate polyols of longer chained linear diols with >4 CH2 repeat units retained higher degrees of crystallinity associated with the polyol soft segment. The ratio of hydrogen bonded urethane in the hard segment to free urethane phase mixed with the soft segment in the TPUs showed a complex oscillating dependence with increased number of CH2 repeating unit in the linear diols of azelate polyols. Correspondingly, static and dynamic properties of TPUs also showed the oscillatory dependence, whereby dynamic properties maximized with odd number of CH2 repeating unit and material strength maximized with even number of CH2 repeating unit. The results therefore can be used as guide to select appropriate azelate polyols to target specific TPU performance. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46258.