The synthesis and characterization of new organosilicon derivatives of N3P3Cl6, N3P3[NH(CH2)(3)Si(OEt)(3)](6) (1), N3P3[NH(CH2)(3)Si(OEt)(3)](3)[NCH3(CH2)(3)CN](3) (2), and N3P3[NH(CH2)(3)Si(OEt)(3)](3)[HOC6H4(CH2)CN](3) (3) are reported. Pyrolysis of 1, 2, and 3 in air and at several temperatures results in nanostructured materials whose composition and morphology depend on the temperature of pyrolysis and the substituents of the phosphazenes ring. The products stem from the reaction of SiO2 with P2O5, leading to either crystalline Si-5(PO4)(6)O, SiP2O7 or an amorphous phase as the glass Si-5(PO4)(6)O/3SiO(2) center dot 2P(2)O(5), depending on the temperature and nature of the trimer precursors. From 1 at 800 degrees C, core-shell microspheres of SiO2 coated. with Si-5(PO4)(6)O are obtained, while in other cases, mesoporous or dense structures are observed. Atomic force microscopy examination after deposition of the materials on monocrystalline silicon wafers evidences morphology strongly dependent on the precursors. Isolated islands of size similar to 9 nm are observed from 1, whereas dense nanostructures with a mean height of 13 nm are formed from 3. Brunauer-Emmett-Teller measurements show mesoporous materials with low surface areas. The proposed growth mechanism involves the formation of cross-linking structures and of vacancies by carbonization of the organic matter, where the silicon compounds nucleate. Thus, for the first time, unique silicon nanostructured materials are obtained from cyclic phosphazenes containing silicon.