In the past few decades, interpenetrating polymer network (IPN) hydrogels have attracted huge attentions due to their special cell-like structures, interpenetrating interface, and two-phase continuity, which has special synergistic effects on performance or function. In this work, eleven different dyes based on 1-aryl-3-(2,4,5trimethoxyphenyl)prop-2-en-1-one or 3-aryl-1-(3,4,5-trimethoxyphenyl)prop-2-en-1one were firstly synthesized, and combined with an amine (i.e. ethyl l,4-(dimethylamino)benzoate, EDB) and an iodonium salt (bis(4-tert-butylphenyl) iodonium hexafluorophosphate, Iod) (PISs) as the three-component photoinitiating systems (PIS) to induce both the free radical photopolymerization (FRP) of polyethylene glycol diacrylate (PEG-DA) and the cationic photopolymerization (CP) of 3,4-epoxycyclohexylmethyl-3',4'-epoxy-cyclohexane carboxylate (EPOX) under the irradiation of LED@405nm. The best candidates were selected from the proposed eleven different dyes to study the involved oxidation-reduction reaction mechanisms 2 through several characterization techniques. The best candidates were also used to prepare PEG-DA/EPOX interpenetrated polymer networks (IPNs). More interestingly, the stable 3D patterns have been successfully produced through direct laser write (DLW) technology, meanwhile, the silver cations could also be reduced in situ into silver nanoparticles. Furthermore, 4D printing could be achieved since all the obtained 3D patterns exhibited reversible swelling properties and shape-memory effect caused by swelling and dehydration processes. Parallel to this, influence of AgNPs on the mechanical properties of the 3D-printed objects and on IPNs has also been systematically studied. Finally, the obtained IPN polymers containing silver nanoparticles (AgNPs) exhibited antibacterial activities for Gram-positive bacteria (e.g. Staphylococcus aureus) and Gram-negative bacteria (e.g. Pseudomonas aeruginosa).