Formation of photoreactive nanomatrix structure was investigated by graft copolymerization of an inclusion complex of 1,9-nonandiol dimethacrylate (NDMA) with β-cyclodextrin (β-CD) onto natural rubber particle using potassium persulfate (KPS), tert-butyl hydroperoxide/tetraethylenepentamine (TBHPO/TEPA), cumene hydroperoxide /tetraethylenepentamine (CHPO/TEPA), and benzoyl peroxide (BPO) as an initiator. The graft copolymer was characterized by 1H-NMR and FT-IR after coagulation. The conversion of NDMA and the amount of residual methacryloyl group was found to be 58.5 w/w% and 1.81 w/w%, respectively, under the suitable condition of the graft copolymerization. The morphology of the film specimen, prepared from the graft copolymer, was observed by transmission electron microscopy (TEM) after staining the film with OsO4. Natural rubber particle of about 1.0 μm in diameter was dispersed in poly(NDMA) matrix of about 10 nm in thickness.