Two new azoxy compounds, 1,3,7-trimethyl-2,6-dioxo-8-azoxymethyl-purine 1 and 1,3,7-trimethyl-2,6-dioxo-8-azoxycaffeine-purine 5 and three known compounds, 1,3,7-trimethyl-2,6-dioxo-8-chloro-purin 2, 1,3,7-trimethyl-2,6-dioxo-8-cyano-purine 3, and 1,3,7-trimethyl-2,6-dioxo-8-amido-purine 4 were synthesized by photochemical reaction of 8-nitrocaffeine under various conditions.