The reaction between hypochlorous acid and chlorite ions is the rate limiting step for in situ chlorine dioxide regeneration. The possibility of increasing the speed of this reaction was analyzed by the addition of tertiary amine catalysts in the system at pH 5. Two amines were tested, DABCO (1,4-diazabicyclo[2.2.2]octane) and its derivative CEM-DABCO (1-carboethoxymethyl-1-azonia-4-aza-bicyclo[2.2.2]octane chloride). The stability of the catalysts in the presence of both reagents and chlorine dioxide was measured, with CEM-DABCO showing to be highly stable with the mentioned chlorine species, whereas DABCO was rapidly degraded by chlorine dioxide. Hence, CEM-DABCO was chosen as a suitable candidate to catalyze the reaction of hypochlorous acid with chlorite ions and it significantly increased the speed of this reaction even at low catalyst dosages. This research opens the door to a faster regeneration of chlorine dioxide and an improved efficiency in chlorine dioxide treatments.