Condensation of ethoxymethyleneamino-thieno[2,3-d]pyrimidines with appropriate amino compounds afforded the corresponding 7-substituted-8-imino-pyrimido[3,2:4,5]thieno[2,3-d]pyrimidines 6a, 6b, and 7 and 2-substitutedpyrimido[3 � ,2 � :4,5]thieno[3,2-e][1,2,4]triazolo[1,5-c]pyrimidines 9a, 9b, respectively. Also, hydrazinolysis of compound 4 in ethanol which yielded the key intermediate 7-amino-8-imino-pyrimido[3,2:4,5]thieno[2,3-d]pyrimidine (10), which can be cyclized with appropriate isothiocyanates 14a-14g in re�uxing pyridine, afforded the corresponding 2-(substitutedamino)-pyrimido[3 � ,2 � :4,5]thieno[3,2-e][1,2,4]triazolo[1,5-c]pyramidines 15a-15g. Furthermore, intramolecular cyclization of compound (10) with appropriate 1,3-dibromopropane and Mannich bases 18a-18c under the basic condition afforded the corresponding (tri)dihydropyrimido[3 � ,2 � :4,5]thieno[3,2:4,5]pyrimido[1,6-b][1,2,4]triazepines 16 and 18a-18c, respectively. On the other hand, the 11-substituted-pyrimido[3 � ,2 � :4,5]thieno[3,2:4,5]pyrimido[1,6-b][1,2,4]triazepines 21a-21e were also obtained by the intramolecular cyclization of compound (10) with appropriate enaminone derivatives 19a-19e under the acidic condition.