In this study, the synthesis of lithium carbonate (Li2CO3) powder was conducted by a carbonation process using carbon dioxide gas (CO2) from waste acidic sludge based on sulfuric acid (H2SO4) containing around 2 wt.% lithium content. Lithium sulfate (Li2SO4) powder as a raw material was reacted with CO2 gas using a thermogravimetric apparatus to measure carbonation conditions such as temperature, time and CO2 content. It was noted that carbonation occurred at a temperature range of 800℃ to 900℃ within 2 hours. To prevent further oxidation during carbonation, calcium sulfate (CaO4S) was first introduced to mixing gases with CO2 and Ar and then led to meet in the chamber. The lithium carbonate obtained was examined by inductively coupled plasma–mass spectroscopy (ICP-MS), X-ray diffraction (XRD) and scanning electron microscopy (SEM) and it was found that of lithium carbonate with a purity above 99% was recovered.