<p>The synthesis and characterization of azide-functionalized soy-based polyols (Az-ESBO) using Amberlyst-15 and Cloisite-20&#xa0;A as solid supports were reported for the first time. The data showed the efficiency of the azide ion as the nucleophile toward both epoxy and ester groups in epoxidized soybean oil (ESBO) under uncontrolled reaction conditions. The research focused on the new optimization of the selective reaction of azide ion with epoxy vs. ester functional groups. The reaction of the azide ion with the ester group causes the loss of the acylglycerol backbone, forming by-products and increasing polydispersity. To enhance the selectivity toward epoxy and/or ester functional groups, the reaction temperature and the amount of NaN₃ (sodium azide) reagent were carefully adjusted (NaN₃: epoxy group = 1:1, 60&#xa0;°C). Moreover, the chemoselectivity of the utilized solid supports was compared. The synthesized Az-ESBO structures were characterized using FT-IR (Fourier Transform Infrared), ¹H-NMR and ¹³C-NMR (Proton and Carbon Nuclear Magnetic Resonance), and GPC (Gel Permeation Chromatography) techniques. The collected data showed a chemoselective synthesis of the ring-opened product in 83% yield when Amberlyst was used as the solid support. The dispersity in molar mass (Đ), M_w, and M_n of the product were calculated as 1.89, 2404, and 1271&#xa0;g·mol⁻¹, respectively. In contrast, Cloisite-20&#xa0;A had a conversion yield of 62% and a dispersity of about three. The ¹H-NMR integral ratio of Az-ESBO was compared to that of ESBO to evaluate the relative selectivity of Amberlyst and Cloisite in preserving the acylglycerol backbone; the corresponding ratio equivalents were 1 and 0.4.</p> Graphical Abstract <p></p>