Nanoskiving, benefiting from its simple operation and high reproducibility, is a promising method to fabricate nanometer-size electrodes. In this work, we report the fabrication of Au nanowire electrodes with different shapes and well-controlled sizes through nanoskiving. Au nanowire block electrodes, membrane electrodes and tip electrodes are prepared with good reproducibility. Steady-state cyclic voltammograms (CVs) demonstrate that all these electrodes behave well as nanoband ultramicroelectrodes. A fast heterogeneous electron transfer rate constant can be extracted reliably from steady-state CVs at various size Au nanowire block electrodes by the Koutecký–Levich (K–L) method. The Au nanowire membrane electrodes demonstrate good sensitivity toward the oxidation of catecholamine and could monitor catecholamine released from rat adrenal chromaffin cells stimulated by high K⁺.