Microelectrodes have been found to be a valuable tool in a variety of analytical studies. Their advantages over macro-sized electrodes are well known, including their enhanced mass transport properties (due to their ubiquitous hemispherical diffusion) which lead to steady state responses without external convection. They also exhibit high signal-to-noise ratios (greater sensitivities), furthering their analytical application. Microelectrode arrays are analytical devices with multiple electrodes. There are suitable for practical sensing with all the benefits of microelectrodes but with greater currents, leading to greater ease of measurement. To produce a reliable electroanalytical device the microelectrode response must be reproducible, a fundamental property based on the quality control of their production. Square microelectrode and array fabrication techniques have been developed for this purpose. This research discusses the fabrication and development of closely spaced arrays of square microelectrodes. Simulated and measured responses are compared and used to characterize electrode and array responses by cyclic voltammetry, electrical impedance spectroscopy and current-time transients. Measurements on variably spaced arrays allow insight into overlap of hemispherical diffusion from individual electrodes and the subsequent effect including peak current output on the array device. By studying these devices key insights into the mass transport properties of single square microelectrodes and microelectrode arrays were gained. This study also prepares and develops microelectrodes from materials appropriate for use in the extreme environments of molten salts and concentrated nitric acid solutions. These robust electrodes were developed for use in hydro- and pyro-chemical techniques for nuclear fuel reprocessing. These results demonstrate the practical uses for microelectrode systems across a wide range of chemical systems and in extreme conditions.