Three new lead(II) N,N‐bis[1(2)H‐tetrazol‐5‐yl]amine (H2bta) compounds, [Pb(bta)(H2O)2]n (1), [Pb2(bta)2(bpy)2] (2), and [Pb2(bta)2(phen)2]·2H2O (3), were synthesized. Single‐crystal X‐ray diffraction reveals that compound 1 has a 1D polymeric zigzag chain structure, whereas compounds 2 and 3 have binuclear structures. In addition, compounds 1–3 were explored as additives to promote the thermal decomposition of ammonium perchlorate by differential scanning calorimetry. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)