A domain-related data search promoted triazolotriazine-fused energetic scaffold filtration with combinatorial design to alleviate the lack of thermostable high-energy materials; 16 candidates were discovered that may show promising energy and safety performance, as well as excellent thermal stability. Novel fused triazolo-1,2,4-triazine energetic material 7-nitro-3-(1H-tetrazol-5-yl)-[1,2,4]triazolo[5,1-c][1,2,4]triazin-4-amine-2-oxide (Candidate No. 4) with excellent thermal stability, high energy performance and low sensitivity was developed successfully by using a facile N-oxide synthetic method. Our findings may be applicable to a wider range of materials and prove equally powerful for searching for other high-performing energetic materials.