With the rapid development of photopolymerization, the search for new near-UV/visible light sensitive photoinitiating system (PIS) is the subject of intense research efforts. In this work, a new PIS (chalcone dye/amine/iodonium salt) could efficiently and simultaneously initiate the free radical photopolymerization (FRP) of PEGDA and the cationic photopolymerization (CP) of EPOX under irradiation of LED@405 nm to obtain interpenetrating polymer networks (IPNs). Then, the study on the photoinitiating abilities of the chalcone dye was examined to explain the chemical mechanisms through UV-visible absorption spectra, cyclic voltammetry, fluorescence approaches and electron spin resonance (ESR) spin-trapping experiments. Markedly, Chalcone is a class of natural dyes of flavonoids with potential low toxicity. Furthermore, this PIS was employed in the photopolymerization of LTA-5A zeolite filled interpenetrating polymer network composites (IPN, PEGDA/EPOX). Compared to the pure IPN, the depth of cure (DOC) for IPN with 50 wt% LTA-5A remarkably increased by ca. 90%, which was the first time reported that DOC could increase with the increase of the filler content. Compared to the storage modulus, tensile strength and Young's modulus of pure IPN, those of the IPN-composites containing 50 wt% LTA-5A increased by ca. 445 %, ca. 430 %, and ca. Commenté [JL1]: Full name (PEGDA) Commenté [JL2]: Full name (EPOX) 2 580 %, respectively. By direct laser write (DLW), 3D patterns could be manufactured and those with high filler contents showed good water swelling property. Under hydrothermal stimuli, IPN composite with 50 wt% LTA-5A exhibited a good 4D printing behavior. Therefore, not only this chalcone dye has a good photoinitiation ability for photopolymerization, but also the resulting IPN composites prepared with the photoinitiating system containing this dye have potential applications for 3D/4D printing and composites preparation.