Catalyst-free, volatile organic solvent (VOC)-free synthesis of biobased cross-linked polymers is an important sustainable feature in polyesterification. To date, these polyesters have been extensively studied for their fundamental sustainability across various uses. The ultimate potential sustainability for these materials, however, is constrained to static structural parts due to their intractable rigid three-dimensional (3D) network. Here, we reveal intrinsic dynamic exchangeable bonds within this type of cross-linked semicrystalline network, poly(1,8-octanediol-