Novel polymer hybrids based on a Ti-containing polyhedral oligomeric silsesquioxane-(Ti)POSS-and two polymer matrices-polyamide 6 (PA6) and a styrene-maleic anhydride copolymer (PSMA)-have been prepared by different approaches (namely, in situ polymerization, melt blending, grafting) in order to investigate the dispersion level of (Ti)POSS within the organic polymer matrices in view of potential in situ catalytic activity of the metal. The chemical characterization of the prepared hybrid systems, performed by infrared spectroscopy and nuclear magnetic resonance, and their morphological analysis, evaluated by electron microscopy and X-ray diffraction, have shown that it is possible to homogeneously distribute and finely disperse (Ti)POSS at nanometric level within PA6 and PSMA. In this manner, an easy incorporation of metal functionalities into the above polymer matrices has been achieved and extension to other polymer systems can be foreseen.