Epoxidised soybean oil (ESO) was cross-linked with an aqueous citric acid (CA) solution without the addition of any other catalyst or solvent. Completely bio-based polymer networks were generated. The initial system was an emulsion, but it became a homogeneous and transparent polymer network by reaction. The ability of the final materials to self-heal without adding extrinsic catalysts was assessed by stress relaxation and lap-shear tests. This was achieved by molecular rearrangements produced by thermally activated transesterification reactions of β-hydroxyester groups generated in the polymerization reaction.