A series of highly cross-linked biopolymers (1-10) was obtained by the copper-catalyzed and the thermal polyaddition of alkynated and azidated soybean oil with suitable diazides and diynes. respectively. Thermal polymerization (heating at 100 degrees C), which requires no catalyst and no solvent, was observed to be a superior approach, yielding polymers (6-10) with more homogeneous cross-linking. The temperature of decomposition of 6-10 was narrower (similar to 170 degrees C) than that of the polymers (1-5) obtained by the copper-catalyzed method (similar to 210 degrees C). The glass-transition temperatures of 1-5 were higher (T-g ranging from 9 to 80 degrees C) than those of the comparable polymers obtained thermally (T-g ranging from 13 to 45 degrees C) because of the catalyst entrapped in the networks of 1-5. Furthermore, the thermal approach requires less time and is higher yielding, establishing the suitability and ease of polymerization of vegetable oil-derived alkynes or azides through thermal "Click" chemistry. The effects of the structure of the monomers and the nature of the linkers on the thermal properties of 1-10 (e.g., T-g and decomposition temperatures) are detailed.