The voltammetry of microparticles and scanning electrochemical microscopy methodologies are applied to characterize praseodymium centers in praseodymia-doped zircon (Pr x Zr(1−y)Si(1−z)O4; y + z = x; 0.02< x <0.10) specimens prepared via sol–gel synthetic routes. In contact with aqueous electrolytes, two overlapping Pr-centered cathodic processes, attributable to the Pr (IV) to Pr (III) reduction of Pr centers in different sites are obtained. In water-containing, air-saturated acetone and DMSO solutions as solvent, Pr x Zr(1−y)Si(1−z)O4 materials produce a significant catalytic effect on the electrochemical reduction of peroxide radical anion electrochemically generated. These electrochemical features denote that most of the Pr centers are originally in its 4+ oxidation state in the parent Pr x Zr(1−y)Si(1−z)O4 specimens. The variation of the catalytic performance of such specimens with potential scan rate, water concentration and Pr loading suggests that Pr is not uniformly distributed within the zircon grains, being concentrated in the outer region of such grains.