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Nanostructured (BiO)2CO3 samples were prepared, and their thermal decomposition behaviors were investigated by thermogravimetric analysis under atmospheric conditions. The method of preparation and Ca2+ doping could affect the morphologies of products and quantity of defects, resulting in different thermal decomposition mechanisms. The (BiO)2CO3 nanoplates decomposed at 300-500 °C with an activation energy of 160-170 kJ/mol. Two temperature zones existed in the thermal decomposition of (BiO)2CO3 and Ca-(BiO)2CO3 nanowires. The first