In this work, we established theoretically that amperometric detector arrays consisting of a series of parallel band microelectrodes placed on the wall of a microchannel may offer excellent analytical detection performances when implemented onto microfluidic (bio)analytical devices after the separative stages. In combination with the concentration imprinting strategies reported in a previous work, these exceptional performances may be extended to nonelectroactive or poorly diffusing analytes. Using an array of electrodes instead of a large single band allows the whole core of the channel to be probed though keeping an excellent time resolution. Thus, analytes with close retention times may be characterized individually with a resolution which eventually outpaces that of spectroscopic detections. Such important advantages may be obtained only through a complete understanding of the complex coupling between diffusional and convective transport of molecules in microfluidic solutions near an electrochemical detector. As a consequence, the conditions underlying the theoretical data presented in this work have been selected after optimizing procedures rooted on previous theoretical analyses. They will be fully disclosed in a series of further works that will also establish the experimental performances of such amperometric detectors and validate the present concept.