The synthetic details for the construction of three new dipyridotetraazapentalene derivatives, 5H-pyrido[3",4":4＇,5＇] [1,2,3]triazolo[1＇,2＇:1,2][1,2,3]triazolo[5,4-b]pyridin-6-ium inner salt (8), 5H-pyrido [3",2":4＇,5＇][1,2,3]triazolo[1＇,2＇:1,2][1,2,3]triazolo[5,4-b]-pyridin-6-ium inner salt (15) and 5H-pyrido[2",3":4＇,5＇] [1,2,3]-triazolo[1＇,2＇:1,2][1,2,3]triazolo[4,5-b]pyridin-6-ium inner salt (16) are presented. Nitration of (8) and (15) afforded the novel tetranitrodipyridotetraazapentalene derivatives, 2,4,8,10-tetranitro-5H-pyrido[3",4":4＇,5＇][1,2,3]triazolo[1＇,2＇:1,2][1,2,3]-triazolo[5,4-b]-pyridin-6-ium inner salt (3) and 2,4,8,10-tetranitro-5N-pyrido [3", 2":4＇,5][1,2,3]triazolo[1＇,2＇:1,2][1,2,3]-triazolo[5,4-b]-pyridin-6-ium inner salt (4) in good yields. Both isomers, (3) and (4), exhibited high thermal stability (differential scanning calorimetric analysis and thermal gravimetric analysis) and were insensitive to impact (hammer/anvil test).