The role of grafting in radiation curing involving CT complexes has been studied using predominantly maleic anhydride (MA) and triethylene glycol divinyl ether (DVE-3) as representative DA components with cellulose and polypropylene (PPE) as substrates. The effect of solvents in the photografting process has been examined in an attempt to optimise the conditions of copolymerisation and the results compared with analogous solvent free systems which simulate curing. The effect of varying the molar double bond ratio of the DA reactants has been investigated since each of the two monomers could be preferentially absorbed by the substrate prior to graft thus affecting their reactivities. The significance of the structure of D and A components in the grafting reaction has been evaluated using different combinations of a variety of monomers. UV and ionising radiation have been compared as initiators of grafting using MA/DVE-3 as reference DA with a range of CT complexes. The D and A components of certain complexes have been used as additives to accelerate the radiation grafting of a conventional monomer like methyl methacrylate (MMA). The significance of all these grafting studies in concurrent radiation curing is discussed. The extension of this technique to the synthesis of new homopolymers, IPNs and composites is evaluated.