Design and synthesis of new energetic materials retains its urgency in chemistry and materials science. Herein, rational construction and regioselective synthesis of a series of energetic compounds comprising of a methylene-bridged combination of 1,2,5-oxadiazole and nitrogen-rich azoles (1,2,4-triazole and tetrazole) enriched with additional explosophoric functionalities (nitro and azo moieties) is presented. All target materials were thoroughly characterized using IR and multinuclear NMR (1H,13C,14N,15N) NMR spectroscopy, high-resolution mass spectrometry, X-ray diffraction,and differential scanning calorimetry. All synthesized energetic substances showed good thermal stability (up to 239oC) and low mechanical sensitivity, while their performance reached or exceeded the level of TNT.