Redox initiating systems (RISs) are highly worthwhile for polymerization in mild conditions (at room temperature-RT) without external thermal or light activation. With high performance redox initiating systems RIS, the free radical polymerization FRP can even be carried out under air and without inhibitors/stabilizers removal from the monomers/resins. However, efficient RISs are still based on peroxides or metal complexes. In this work, a pure organic and peroxide-free RIS is presented based on the interaction of a well-selected triarylamine derivative (T4epa) with iodonium salt used as reducing and oxidizing agents, respectively. The redox polymerization (Redox FRP) was followed through pyrometry and thermal imaging experiments. Remarkably, a full control of the work time as well as a high reactivity is observed for mild conditions.