Novel photocurable ternary polymer networks were prepared by incorporating N-(4-hydroxy-3-methoxybenzyl)-acrylamide (HMBA) into a cross-linked thiol−ene network based on poly(ethylene glycol) diacrylate (PEGDA) and (mercaptopropyl) methylsiloxane homopolymers (MSHP). The ternary network materials displayed bactericidal activity against Escherichia coli, Staphylococcus aureus, and reduced the attachment of marine organism Phaeodactylum tricornutum. Extensive soaking of the polymer networks in aqueous solution indicated that no active antibacterial component leached out from the materials, and thus the ternary thiol-ene coating killed the bacteria by surface contact. The surface structures of the polymer networks with varied content ratios were studied by sum frequency generation (SFG) vibrational spectroscopy. The results demonstrated that the PDMS Si-CH3 groups and mimic-capsaicine groups are predominantly present at the polymer-air interface of the coatings. Surface reorganization was apparent after polymers were placed in contact with D2O: the hydrophobic PDMS Si-CH3 groups left the surface and returned to the bulk of the polymer networks, while the hydrophilic PEG chains cover the polymer surfaces in D2O. The capasaicine methoxy groups are able to segregate to the surface in an aqueous environment, depending upon the ratio of HMBA/PEGDA. SFG measurements in situ showed that the antibacterial HMBA chains, rather than the “non-fouling” PEG, played a dominant role in mediating the antibiofouling performance in this particular polymer system.