A novel approach to highly ordered and modular nanoelectrode arrays (NEAs) has been developed using block copolymer self-assembly. Variable scan rate cyclic voltammetry studies were performed to characterize the NEA. At low scan rates, the NEA behaves similar to a macroelectrode, while at high scan rates the nanoelectrodes act independently. This is an important feature for real-time in vivo sensing and other electroanalytical applications.