Novel nanoelectrode fabrication technologies have been developed to provide higher spatial and faster temporal measurements of small molecules associated with cellular function; specifically those involved in neuronal communication. Enhancement of spatiotemporal resolution is a direct result of restricted diffusion and molecular confinement at nanoscale electrochemical elements. We have developed a method using focused-ion beam (FIB) to mill through ~5-µm thick insulating layers of poly(methylmethacrylate) (PMMA) to fabricate nanoelectrode templates. FIB milling is a technique that provides precise spatial control of nanoscale fabrication. Such control allows for fabrication of single pore electrode templates as well as multiple pore array templates. In situ characterization of these templates and electrode architectures is performed using SEM imaging. PMMA nanoelectrode templates are affixed to commercially available macroelectrodes (3 mm dia.) using colloidal conductive graphite adhesive. The template is sealed to the electrode using partially cured poly(dimethylsiloxane) allowing for full submersion of the electrode. Recently obtained data using cyclic voltammetry at single nanoelectrodes suggests recessed-well, inlaid-disk, and recessed-disk nanopore constructs are probing unique nanoscale electrochemical phenomenon, such as restricted diffusion. Non-typical responses of certain electrochemical couples such as potassium ferrocyanide suggest that in addition to restricted diffusion arising from reduced electroactive area, residual surface charge on PMMA cause electrostatic interference of expected diffusion at nanopore constructs.