Biofuel cells (BFCs) use either enzymes or bacteria to catalyse a fuel to generate power. Their advantages over conventional fuels is that they do not use precious metals and the high selectivity of biocatalysts mean that no separation membranes are required between the electrodes. However, the application of BFCs is limited by their low power output and poor enzyme lifetimes. This thesis addresses these limitations by investigating aligned carbon nanotubes (aCNTs) as potential electrode materials. These aCNT electrodes offer high surface areas to increase enzyme coverage and hence power output and their surface topology can stabilise the enzymes to ensure maximum lifetime and current density.A novel BFC half cell was developed using aCNTs and the fungal enzyme, Trametes versicolor laccase which catalyses the four-electron reduction of oxygen to water. Laccase was shown to communicate directly with the nanotubes enabling the oxidant reduction reaction to be monitored without the need for mediators. Initial investigations compared aCNTs with other commonly reported carbon electrodes and found that the current densities were ~30-fold higher on the aCNTs than at pyrolytic graphite edge electrodes. The high surface area of these electrodes contributed to greater electroactive coverage of enzyme and minimal loss of enzyme upon deposition. Cathodic currents increased linearly with geometric electrode area; however they did not scale with actual electrode surface area and the current density was limited to the order of μA cm-2 due to O2-transport limitations. It was also discovered that the porous contribution of these aCNT electrodes could lead to misleading interpretations on nanotube electrochemistry. This effect was observed when increments in electrode area resulted in apparently significantly faster kinetics. This improvement in catalytic behaviour was proposed to be due to a transition from mass diffusion limited to thin layer cell behaviour exhibited by porous materials. Thermal pretreatment of the aCNT electrodes in oxidative and reductive atmospheres were found to improve their performance. These treatments worked by changing the nanotube surface chemistry and purifying the nanotubes, as evidenced by various physical characterisation methods. Furthermore, laccase activity was enhanced significantly after electrodes had been treated under both atmospheres, where it was believed that the removal of contaminant material and higher defect densities increased electrochemical performance.Finally, mass transport limitations were addressed by developing micro-patterned aCNT electrodes which possessed channels in the arrays, allowing better oxygen diffusion. Fundamental studies showed higher current densities per surface area and thus represent a promising electrode for future BFC research.