In this work, the electrogeneration of peroxodisulfate from a 1 M H2SO4 solution on boron-doped diamond microelectrodes array has been studied. The peroxodisulfate is detected at the vicinity of the boron doped diamond electrode, with the SECM probe, only when the polarization of the microarray is greater than 2.1 V versus AgCl/Ag. The main electrochemical interest of working with microarrays comes from the fact that current densities and efficiencies are comparable to those observed in the peroxodisulfate industrial production. The local Scanning Electrochemical Microscopy studies have shown that the peroxodisulfate reaction is related to a surface mediated oxidation of sulfate anions into peroxodisulfate according to a complex reactional mechanism.