The development of biofunctionalyzed nanostructured materials for enzyme immobilization with applications in biotechnology, biocatalysis and biosensors is an emerging area of research. In this presentation, we report spontaneous formation of microfibers of nanostructured polymer composites in aqueous media and their application to enzyme immobilization and biosensors. The enzyme immobilized on this material remains fully active during manufacturing, storage and use. In the first part of the presentation, we will focuss on the (1) synthesis of the nanostructured composites, (2) mechanism of enzyme immobilization, (3) study of biocatalytic activity and Michaelis-Menten kinetic and (4) the optimal conditions necessary to obtain a good functionality and stability of the biofunctionalyzed nanostructure. Finally, we will discuss the application of this material for the construction of an amperometric enzyme biosensor for the detection of glucose.