The functionalization of S-1% DVB copolymer was carried out with aminophosphonate groups, and then the samples were covered with silica to obtain hybrid materials. The obtained hybrid materials were used as supports for impregnation of transition metal ions [Cu(II) and Mn(II)], and they were subsequently used as catalysts in oxidation reactions. The supports and catalysts were characterized by FTIR and UV-Vis spectroscopy, thermal analysis, SEM, and TEM electron microscopy. The results of FTIR spectroscopy indicated the formation of a hybrid of silica and an aminophosphonate polymer by the sol-gel route. The UV-Vis spectra showed a strong interaction of Cu(II) and a weak interaction of Mn(II) with aminophosphonate groups of the supports. The catalytic tests confirm different interactions between the metal cations and obtained supports. The formation of the immobilized Cu(II) complexes shows the possibility of using these materials selectively in oxidation of various organic compounds (anisole, cyclohexene, toluene, styrene, phenol). The purpose of this article is to develop some new poly(aminophosphonates)/silica hybrid materials immobilized with transition metal such as Cu(II) and Mn(II) ions for future use in the oxidation process.