Amino-functionalized organic-inorganic hybrid materials with a narrow distributed nanostructure of 2-4 nm in size were obtained by means of a template-free and non-aqueous procedure. Simultaneous twin polymerization of novel amino group containing twin monomers with 2,2'-spirobi[4H-1,3,2-benzodioxasiline] has been applied for this purpose. The amino groups of the organic-inorganic hybrid material are useful for post derivatization.