AbstractA review is attempted of the inorganic redox systems in the context of free radical graft polymerization. Metal ion‐H2O2 redox systems are considered as part of the spectrum of such inorganic and organic reagents used for the purpose. It is emphasized that the chemistry of these latter systems in particular is much like the radiation chemistry of aqueous solutions caused by high energy ionizing radiations. On the other hand, these systems involve low energy and therefore are less damaging to the substrate and relatively more specific. The reactivity of free radicals in these systems varies subtly with the system and the medium. It is observed that only ceric ion method and [Fe(II); Fe(III)] ‐H2O2 system are most successful in grafting onto cellulosic materials. Attention is paid to the features which makes these systems so useful. Concrete results from ESR study are presented which underline the nonspecific nature of various free radical producing systems including radiati