Kinetic studies were performed to clarify the Kornblum-Delamare reaction mechanism of bicyclic endoperoxides. Ascaridol and 1,4-diphenyl-2,3-dioxa-bicyclo[2.2.2]oct-5-ene, not having alpha-protons, did not provide any reaction with bases. Reaction with different bases has revealed that reaction rates for the base-catalyzed decomposition of 2,3-dioxa-bicyclo[2.2.2]oct-5-ene depend strongly on the base strength. The stronger the base used, the faster the conversion rate. Reaction rate values k of endoperoxides with different skeletons were also studied with NEt3. It has been noted that the strength of the base plays the dominant role in determining the rate of the reactions.