This study reported red-purple staining of light-exposed, root-treated dentin when root canals were rinsed with 1.3% NaOCl as initial rinse followed by the use of BioPure MTAD as final rinse. This intrinsic dentin staining occurred irrespective of whether the root canals were filled, and could be observed even in crown dentin when the latter was sequentially immersed in NaOCl and MTAD. Bench-top reproductions of the phenomenon revealed that the exothermic reaction is not an acid-base reaction. Conversely, the reaction is of a redox nature that highly resembled the previously reported mechanism of tetracycline staining, in which photo-oxidation of tetracycline resulted in a red-purple tetracycline degradation product that has a high affinity for hydroxyapatite. This photo-oxidative degradation process is probably triggered by the use of NaOCl as an oxidizing agent, and may be prevented by rinsing the NaOCl-treated dentin with ascorbic acid, a reducing agent, before the application of MTAD.