In this study, an environmentally benign electrochemical protocol for intramolecular oxidative amination is developed, which offers an efficient and sustainable route to access diverse fused tricyclic systems of pyrido[1,2-e]purine-2,4-dione derivatives with pharmacological interest, exhibiting broad scope and generality (>50 examples, yields up to 99%). This electrochemical strategy features good functional group tolerance and permits access to compounds that were previously not achievable under thermal conditions. The photoluminescence properties of the representative N9-fused tricyclic xanthines have also been investigated.