||This study describes a template-mediated self-assembly synthesis, full characterization, and structural features of two new silver-based bioactive coordination polymers (CPs) and their immobilization into acrylated epoxidized soybean oil (ESOA) biopolymer films for antimicrobial applications. The 3D silver(I) CPs [Ag-4(mu(8)-H(2)pma)(2)](n)center dot 4nH(2)O (1) and [Ag-5(mu(6)-H(0.5)tma)(2)(H2O)(4)] (n)center dot 2nH(2)O (2) were generated from AgNO3 and pyromellitic (H(4)pma) or trimesic (H(3)tma) acid, also using N,N -dimethylethanolamine (Hdmea) as a template. Both 1 and 2 feature the intricate 3D layer-pillared structures driven by distinct polycarboxylate blocks. Topological analysis revealed binodal nets with the flu and tcj/hc topology in 1 and 2, respectively. These CPs were used for fabricating new hybrid materials, namely, by doping the [ESOA](n) biopolymer films with very low amounts of 1 and 2 (0.05, 0.1, and 0.5\%). Their antimicrobial activity and ability to impair bacterial biofilm formation were investigated in detail against both Gram-positive (Staphylococcus epidermidis and Staphylococcus aureus) and Gram-negative (Pseudomonas aeruginosa and Escherichia coli) bacteria. Both silver(I) CPs and derived biopolymer films showed activity against all the tested bacteria in a concentration-dependent manner. Compound 1 exhibited a more pronounced activity, especially in preventing biofilm growth, with mean bacterial load reductions ranging from 3.7 to 4.3 log against the four bacteria (99.99\% bacterial eradication). The present work thus opens up antibiofilm applications of CP-doped biopolymers, providing new perspectives and very promising results for the design of functional biomaterials.