Chemical analysis is being performed in devices operated at ever decreasing length scales in order to harness the fundamental benefits of micro and nanoscale phenomena while minimizing operating footprint and sample size. The advantages of moving traditional sample or chemical processing steps (e.g. separation, detection, and reaction) into micro- and nanofluidic devices have been demonstrated, and they arise from the relatively rapid rates of heat and mass transport at small length scales. The use of electrochemical methods in microanoscale systems to control and improve these processes holds great promise. Unfortunately, much is still not understood about the coupling of multiple electrode driven processes in a confined environment nor about the fundamental changes in device performance that occur as geometries approach the nanoscale regime. At the nanoscale a significant fraction of the sample volume is in close contact with the device surface, i.e. most of the sample is contained within electronic or diffusion layers associated with surface charge or surface reactions, respectively. The work presented in this thesis aims to understand some fundamental different behaviors observed in microanofluidic structures, particularly those containing one or more embedded, metallic electrode structures. First, a quantitative method is devised to describe the impact of electric fields on electrochemistry in multi-electrode microanofluidic systems. Next the chemical manipulation of small volumes (≤ 10-13 L) in microanofluidic structures is explored by creating regions of high pH and high dissolved gas (H2) concentration through the electrolysis of H2O. Massively parallel arrays of nanochannel electrodes, or embedded annular nanoband electrodes (EANEs), are then studied with a focus on achieving enhanced signals due to coupled electrokinetic and electrochemical effects. In EANE devices, electroosmotic flow results from the electric field generated between the closely spaced working and counter electrode, causing beneficial convective transport to the electrode surface. Finally, redox cycling of electroactive species at recessed ring-disk nanoelectrode arrays is described with a focus on the use of finite element calculations to predict electrode performance as a function of electrode geometry. The improved understanding of electrochemistry, electrokinetics and mass transport in micrometer and nanometer scale structures presented in this thesis should guide the development of next-generation devices for combinatorial processing involving electrochemical analysis, reagent generation and heterogeneous reaction.