The immobilization of redox proteins on electrode surfaces has been crucial for understanding the fundamentals of electron transfer in biological systems and has led to the development of biosensors and other bioelectronic devices. Novel materials, such as carbon nanotubes, gold and other metallic nanoparticles, carbon nanofibre and mesoporous materials have been widely used in the construction of these bioelectrodes, and have been shown to greatly improve the efficiency of electron transfer between the electrode and the redox centre of the protein. The use of these materials has spawned a diversity of covalent and non-covalent techniques for protein immobilization that offer different advantages and disadvantages to the performance of the bioelectrode. This review covers the important properties of these novel electrode materials relevant to the bioconjugation of proteins, and discusses the various methods of attachment from recent examples in the literature.