Biofuel cells, and among them enzymatic biofuel cells, are expected to take part in a sustainable economy in a next future. The development of such biodevices requires significant improvements in terms of efficiency of enzyme immobilization at the electrodes, so as to enable direct electron transfer, and to increase and stabilize the current densities. Many works during the last years aimed at reaching higher current densities, thus power densities, while increasing the long term stability of the enzymatic bioelectrodes. Search for new enzymes, wild type or mutants, new entrapment procedures, but also new electrode architectures, have been targeted. This review focuses on the materials developed and involved during the last few years to meet these demands via nanostructuration of electrode interfaces. Discussion is essentially focused on cases where direct electron transfer between enzymes and electrochemical interfaces are involved. After having introduced the main reasons for the need of nanostructuration, the materials and methods that are newly developed are described. The consequences on improved performances for enzymatic bioelectrodes are discussed, and finally major challenges for future research are addressed.