The differences in the mechanism of the halogenate reactions with the same oxidizing/reducing agent, such as H2O2 contribute to the better understanding of versatile halogen chemistry. The reaction between iodate, bromate, and chlorate with hydrogen peroxide in acidic medium at 60 degrees C is investigated by using the electron paramagnetic resonance (EPR) spin trapping technique. Essential differences in the chemistry of iodate, bromate, and chlorate in their reactions with hydrogen peroxide have been evidenced by finding different radicals as governing intermediates. The reaction between KIO3 and H2O2 is supposed to be the source of IO2 radicals. The KBrO3 and H2O2 reaction did not produce any EPR signal, whereas the KClO3H2O2 system was found to be a source of HO radical. Moreover, KClO3 dissolved in sulfuric acid without hydrogen peroxide produced HO radical as well. The minimal-core models explaining the origin of obtained EPR signals are proposed. Current findings suggested the inclusion of IO2 and HOO radicals, and ClO2 and HO radicals in the particular kinetic models of iodatehydrogen peroxide and chloratehydrogen peroxide systems, as well as possible exclusion of BrO2 radical from the kinetic scheme of the bromatehydrogen peroxide system. Obtained results may pave the way for understanding more complex, nonlinear reactions of these halogen-containing species.