Two series of 18 new dyes selected from in silico molecular design (i.e.through molecular orbital calculations) were synthesized and used in conjunction with an amine (i.e. ethyl l,4-(dimethylamino)benzoate, EDB) and an iodonium salt (bis(4tert-butylphenyl)iodonium hexafluorophosphate, Iod) as photoinitiating systems (PISs) capable of initiating the free radical polymerization of polyethylene glycol (600) diacrylate (PEG-diacrylate) and the cationic polymerization of 3,4epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (EPOX) via an oxidationreduction reaction mechanism. Even though most of these dyes exhibit excellent light absorption properties below 380 nm, the photopolymerization efficiency of acrylates carried out under LED@405 nm are much better than that reached with a LED@375 nm both in thin films and thick films. Furthermore, all of them can also boost the cationic polymerization of EPOX upon LED irradiation at 405 nm, in the presence of an iodonium salt and an amine. More interestingly, stereoscopic 3D patterns were successfully fabricated by the laser writing technique which demonstrated reversible swelling properties and reversible shape-memory effects induced via swelling and dehydration for the access to 4D printing.