Ceramic has been used to store and package Baijiu for thousands of years in China. The dissolution of heavy metals from ceramic packaging has effects on Baijiu quality and human health. However, there are few reports on the dissolution mechanism of heavy metals from ceramic packaging of Baijiu. The distribution of heavy metals dissolution from ceramic packaging and its influence factors were summarized in this paper. The cosolvent and colorant containing heavy metals were probable the main dissolution sources based on the analysis of composition of ceramic glaze. The related limitation and test standards of heavy metals dissolution from ceramic in the world were compared and Pb and Cd were mostly focused in these standards. However, the research results showed that the dissolution of Zn and Ni from ceramic packaging should not be neglected. The ingredients, ratios and thickness of glaze were the main factors affecting the dissolution of heavy metals from ceramic packaging as well as pH and alcohol concentration of Baijiu. Ion exchange and dissolution of glass matrix were considered as the principal mechanisms of Pb from the ceramic packaging. Moreover, it indicated that high alcohol concentration of Baijiu was in favor of decreasing the acid formation and inhibiting the dissolution of heavy metals. The interaction mechanisms between acid, alcohol and ester in Baijiu and heavy metals in ceramic should be further researched to provide a basis for reducing and controlling the heavy metal dissolution during the production of ceramic packaging and the whole process of Baijiu storing and consuming.