(Science China Press) In this work, guanidine cation CN3H6+ and 3-amino-1,2,4-triazole C2H4N4 were crystallized into NaN5 and two novel energetic coordination polymers (CPs), (NaN5)5(CH6N3)N53- and (NaN5)2(C2H4N4) were prepared respectively via a self-assembly process. The decomposition temperatures of both polymers increase to 118.4 and 126.5°C respectively. Moreover, no crystallized H2O was generated in products to afford the anhydrous compounds of pentazole salts as promising energetic materials.