We conducted the first-ever investigation on the use of amphipathic triphenylmethane dyes ethyl violet (EV), in combination with iodonium salts (Iod) and sodium tetraphenylborate (STPB), as novel visible light photoinitiating systems (PISs), for initiating oil-based photopolymerization of acrylate and thiol-ene, as well as water-based photopolymerization, under 630 nm and 450 nm light-emitting diodes (LED) irradiation. The polymerization kinetics verified the efficient initiation of the EV/STPB/Iod system under two light sources. Differential scanning calorimetry (DSC) and thermal imaging tests further confirmed the crucial role of light in the polymerization process. The potential photolysis mechanism of these systems containing EV was explored through steady-state photolysis, liquid chromatography-mass spectrometry (LC-MS), and electron spin resonance (ESR). This research not only offers a viable approach for developing PISs used for LED photopolymerization technology but also contributes to the development of water-based photopolymerization.