A few of novel, thermally stable, nitro-substituted calixanes were successfully synthesized and their spatial configurations also were confirmed. 1(4),1(6),3(4),3(6),5(4),5(6),7(4),7(6)-octanitro- 2,4,6,8-tetraoxa-1,3,5,7(1,3)-tetraben-zenacyclooctaphane (7) as heat-resistant explosives can be prepared by means of a facile synthetic produced and shows outstanding properties (good thermal stability and high thermal decomposition temperature and energetic per-formances). It has also been pointed out that the production of compound 7 is very easy on a large scale. All target compounds was characterized by single-crystal X-ray diffraction, NMR and elemental analysis, TG and DSC. In this paper, the macrocyclic compounds are introduced into the study as heat-resistant explosives firstly, which will change the past stagnant situation!