Of particular interest to the preparation of advanced materials is synthesis and characterization of carbon nanostructures (e.g. nanotubes) and noble metal nanoparticles, their stabilization (e.g. through self-assembly), as well as organization into two-dimensional arrays and controlled fabrication (e.g. through the sequential attraction) into three-dimensional network films. They can form nanosized materials with well-defined composition, structure and thickness. The interfaces can be also highly functionalized, and they can exhibit specific catalytic or unique electronic, charge storage, optical and sensing properties. We explore here the ability of inorganic structures to stabilize and derivatize metal and carbon nanostructures. Among inorganic systems, polyoxometallates of molybdenum and tungsten are attractive since they can not only adsorb irreversibly on solid surfaces but also exhibit reversible stepwise multielectron transfer reactions. The concept of the layer-by-layer formation of hybrid (organic-inorganic) assemblies composed of anionic polyoxometallate-protected carbon nanotubes (or metal nanoparticles) and ultra-thin films of positively charged conducting polymers (e.g. such as polyaniline or PEDOT) will be described and discussed here. The resulting novel composite materials have been fabricated as thin or moderately thick (µm level) films on electrode surfaces. As evidenced from STM and scanning electron microscopy, their morphology is still granular but the structure is fairly dense. Further, they are characterized by fast dynamics of charge propagation. Obviously, this research is of importance to the construction of effectively operating charge storage devices (capacitors), charge mediators (e.g. in bioelectrochemistry), molecular electronic systems and electrocatalysis. In the latter case, polyoxometallates can also be applied to stabilize and link Pt-Ru, Pt-Sn and various alloyed Pt-based nanoparticles. It is apparent from diagnostic cyclic voltammetric, rotating disk voltammetric and chronoamperometric measurements that such systems exhibit attractive properties towards electroreduction of oxygen or oxidation of alcohols (ethanol, methanol). Here, it is possible that addition of polytungstate or molybdate clusters to ruthenium or tin hydroxo species at the catalytic interface results in activating effect on dispersed platinum particles. An alternate explanation may involve a possibility of electronic effects and/or different morphologies of the catalytic films in the presence and absence of polyoxometallate.