In this study, the cerium(III) trifluoromethanesulfonate-catalyzed cycloaddition of 1,4-naphthoquinone with functionalized azides in aqueous solutions was used to synthesize naphtho[2,3-d][1,2,3]triazole-4,9-dione derivatives. Moreover, our method boasts scalability and completes the synthesis of two key biological compounds. Our method's advantages are environmentally friendly reaction conditions, easy applicability in large-scale operations, broad structurally diverse products produced in high yields, and the recyclability of catalysts.