The anti-biofouling properties have important applications in the medical field. In this study, cross-linked networks were prepared by photopolymerizing two synthetic macromonomers, including fumaric acid monoethyl ester (FAME) functionalized, three-armed poly(L-lactide) prepolymers (3-PLLA-F) and poly(ε-caprolactone) prepolymers (2-PCL-F), with N-vinyl-2-pyrrolidone (NVP) as the diluent. The prepared networks were characterized by their thermal properties, mechanical properties, cytotoxicity experiments and anti-biofouling properties. The Young's modulus and tensile strength of networks decreased by increasing PCL content. In contrast, the elongation of networks significantly increased. Moreover, no obvious cytotoxicity was observed, and the adhesion of L929 fibroblasts and platelets was resisted. Combined with Digital Light Processing technology (DLP) in the future, the designed polymer network could potentially be commercial in the field of biological anti-fouling materials.