Exploration of advanced lead-free primary explosives is a challenging issue in the field of energetic materials. Herein, we designed and synthesized a novel N-rich copper bromate energetic coordination compound (ECC) [Cu(ATRZ)(BrO3)2]n (BLG-1, ATRZ: 4,4'-azo-1,2,4-triazole) by a simple one-step reaction. BLG-1 is the first reported three-dimensional (3D) N-rich copper bromate ECC. Its interesting 3D reticular architecture contributed to its highest thermal decomposition temperature (Td: 226 °C) and crystal density (ρ: 2.69 g cm-3) among N-rich copper bromate ECCs. More importantly, a primary charge of BLG-1 as little as 3 mg could reliably detonate compressed RDX, and 1 mg could detonate CL-20. These incredible values indicated that BLG-1 had an ultra-powerful initiating ability far superior to that of previously reported primary explosives. BLG-1 had improved mechanical sensitivities (IS: 13 J; FS: 1 N) and electrostatic sensitivity (EDS: 240 mJ) compared with those of the typical lead-based primary explosive, lead azide (IS: 4J; FS: 0.75N; EDS: 5 mJ). In particular, BLG-1 had a low laser-initiation threshold of 13 mJ at 808 nm, suggesting that it could serve as a laser-ignitable primary explosive. This work suggests that BLG-1 is a promising candidate with engreat practical application prospects for lead-free primary explosives.