This work investigates the influence of the precursor trimethylsilil isocyanate on the sol-gel synthesis of hybrid materials. The obtained Si−O−C−N network is additionally modified by titanium and zirconium alcoxypropoxides in the range of 10 to 30 wt. %. The structure of the obtained hybrid materials before and after pyrolysis up to 1100°C was investigated by methods of XRD, FTIR and 29Si MAS NMR. We established that the hybrid structure was stable up to 600°C based on IR study. The structural transformation of the hybrid materials into oxycarbonitrogen system started at 800°C. The network of the hybrids modified by titanium remained stable and amorphous up to the final temperature of the pyrolysis (1100°C) compared to the gels modified by more than 10 wt.% Zr. It was confirmed by XRD analysis that the last mentioned are nanocomposite materials, built from carbooxynitrogen vitreous matrix and ZrO2-nanocrystals (tetragonal). The NMR method verified the presence of heterometallic bonds (Si−O−Ti and Si−O−Zr) and Q4, ZrQ3 or TiQ3, NSiO3 and D structural units in the gels.