Eight energetic salts with a gem-dinitro group based on 1,2,4-oxadiazole were developed. All of the structures were confirmed by infrared (IR) spectroscopy, ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy, and high-resolution mass spectrometry (HRMS), and single-crystal X-ray diffraction was used to determine the structures of the pivotal intermediate 3-(chlorodinitromethyl)-5-methyl-1,2,4-oxadiazole (3), the potassium salt (4) and the hydrazinium salt (7). All of them are insensitive to impact (>40 J) and have higher energy levels than trinitrotoluene (TNT).