A miniaturized, packed-bed, continuous-flow reactor to carry out the enzymatic interesterification of ethyl acrylate with diverse allyl aliphatic esters is described. CALB (lipase B from Candida antarctica immobilized on a macroporous acrylic resin) was used as a biocatalyst in a solvent-free system. Allyl acrylate was produced with a conversion of 45% and productivity of 48.3 mg (g biocatalyst)−1 min−1. Then, polymeric materials were prepared from mixtures of acrylate esters. Copolymerization was achieved both in bulk and using water as the solvent. Depending on the polymerizing system used, polymerization yields were 83% and 70% after 2 h and 18 h, respectively. Successful synthesis in a miniaturized continuous-flow reactor allows the use of allyl esters obtained from renewable sources as starting materials.