Elementally Chlorine Free (ECF) bleaching will be superior than Totally Chlorine free (TCF) bleaching, not only because they have no significant difference in effluent toxicity, but also those pulps bleached by ECF have higher brightness, strength, yield, etc., over those by TCF. With this belief, this paper focused on the chemistry of chlorine dioxide decomposition and ionization, both in water solution and in pulp slurry. Special attention was paid to chlorate ion because there have been controversies as how it is formed and what its behavior to the end pH of pulp bleaching is. As a result, during ionization of chlorine dioxide with water, both chlorate and chlorite were found to increase with increasing pH, but during ionization with pulp, chlorite was found to increase with end pH while chlorate decreased with increasing end pH. In the case of ionization with water, the disproportion equation $2CIO_2 + OH^{-} lightarrow H_2O + CIO_3^{-} + CIO_2^{-}$ was thought to become the main reaction with the increasing pH, while in the case of ionization with pulp, the reaction $HCIO + CIO_2^{-}lightarow H^{+} + Cl^{-} + CIO_3^{-}$ was the main reaction contributing to the formation of chlorate. Based on this above opinion, the contrary results of chlorine dioxide ionization from different researchers were discussed and explained.