Design of novel composite materials nowadays is largely based on the synthesis of tailored nanolevel structures and their subsequent integration in the purposefully selected polymer matrices. Additives, such as graphite, graphene and carbon nanotubes, gain especial attention by considering their unique thermal, electrical and mechanical properties. It is, however, important to avoid nanofiller agglomeration during processing as well as to ensure sufficient interfacial adhesion with polymer matrix. These aims can be achieved by regulation of the interactions in the polymer matrix-nanofiller interface by purposeful covalent or non-covalent modification of the constituents of the multi-component system in situ or ex situ. Considering previously mentioned statements, the current research is devoted to investigation of the effects of organically modified carbon nanofillers on the structure and performance of polyvinylalcohol (PVOH), broadly used in industrial adhesive, textile, paper and other industries. Graphite (G), graphite oxide (GO), reduced graphite oxide (RGO) and their organically modified (OM) counterparts have been introduced in the PVOH matrix within broad concentration range (0.1 to 5 wt.%). The nanocomposites have been obtained by means of solution casting method. Nanocomposites design and manufacturing parameters has been optimized. Especial attention has been paid to optimization of film forming behaviour of the nanocomposites. X-ray diffraction measurements, morphological characterization, thermogravimetric analysis, thermo-physical properties characterization, dielectric measurements and dynamic mechanical thermal analysis have been performed to characterize structure and some exploitation characteristics of the manufactured PVOH matrix nanocomposites.