Pyrolysis of the mixtures: [NP(0(2)C12H8)]n // AuCl(PPh2) system (I) [NP(O2C12H8)]0 8[NP(OC6H4CH2CN.{Ru])2]015 NP(OC6H5)10C6H4CH2CN. [Ru] 0.05]n // 'BuSiMe2Cl system (II) and N3P3[NH(CH2)3Si(OEt)3]6// N3P3[OC6H4CH2CN. TiCp2Cl]6(PF6)6 system (III) were studied in air and at 800 °C, and their products characterized. Nanostructured Au foams; Ru0(2) and Ti(P0(3))3 islands deposited on SiP(2)0(7) / P(4)0(7) matrix respectively were obtained. System (I) affords similar results to the pyrolysis of the polyphosphazene having the AuCl(PPh2) coordinated to the polymeric chain which can be attributed to a probable coordination of the Au fragments to the polymer during the heating process. In the system (II) the no presence of metallic nanostructures containing Si was attributed to the absence of Si ultraestructures due to the no cross-linking of the precursor by volatilization of the silicon molecular compound. In the system (III) the ciclic trimer acts each one as template for the formation of mesostructured products remaining separated at the micro level