Electrostatically assembled organic-inorganic hybrid nanostructures based on mineral nanoparticles, carbon nanotubes and polymers/oligomers have been investigated in this work. Depending on the nature of the elementary building blocks, different types of complexes are formed, including stable singlet nanocolloid, core-shell coacervates, fractal aggregates and decorated tubes. They possess interesting bulky and interfacial properties which can be used for generating functional interfaces and materials. The influence of the formulation process/pathway on the nanostructure and morphology of these hybrid complexes is then discussed; the possibility of developing a large variety of morphologies from limited chemicals is highlighted. Finally, the spontaneous and controlled growth of heterostructured materials directly from an interface is reported and several hypotheses on the mechanism are put forward. This approach is suggested to be used in surface functionalization and patterning applications.