Boron doped diamond microelectrodes arrays (MEA) have been prepared in order to be used as new amperometric sensors in electrochemical cells for HPLC detectors. The following parameters were studied: number and diameter (15–40 µm) of the electrodes, distance between them (50–240 µm), and effect of the flow rate (0.1–3 mL/min). It was thus possible to find the optimum value of the parameters which give a good signal/noise ratio in the chronoamperometric responses, with a size of the electrochemical sensors as small as possible.