The early Cambrian stratiform massive barite in southern China is one of the largest barite metallogenic provinces in the world. It includes two major metallogenic belts – the Qinling-Daba and the Jiangnan metallogenic belt – spatially distributed along the northern and eastern margins of the Yangtze platform, respectively. Based on the biogeochemical cycle of barium in the modern ocean, this paper described the geological characteristics of typical barite deposits in the Qingling-Daba and the Jiangnan belts. In particular, the similarities and differences in the mineralogical and geochemical composition of barite deposits from the two metallogenic belts are discussed. Similar geochemical and stable isotope composition suggest that barite deposits of the two metallogenic belts may have the same barium sources and deposited in a similar paleoceanographic environment. During the early Cambrian, the high primary productivity in the ocean around the Yangtze platform enhanced the barium accumulation in the seawater, providing the prerequisite for massive barite deposition. The sulfate concentration and spatial distribution in the ocean are the significant factors controlling the precipitation of the barite. The diagenetic process not only caused the dissolution, migration and recrystallization of deposited barite, but also responsible for the mineralization zonation of barite and witherite in the Qinling-Daba metallogenic belt. Compared to the barite deposits, the deposition of witherite may involve methanogenesis contributed by the organic matter degradation and production of carbonates from the anaerobic oxidation of methane. Although intensively studies, as yet, the barium sources, paleoceanographic environment, and diagenetic processes of the early Cambrian massive barite deposits in south China need to be further discussed, such as the contribution of hydrothermal overprinting and cold seep activities to the formation of barite and witherite deposits, the primary productivity and sulfate concentration of the seawater during the early Cambrian. Prospectively, the barium sources, paleoceanographic environment, and diagenetic processes could be better constrained and characterized by the detailed comparison of the Qinling-Daba and the Jiangnan metallogenic belt through in-situ Sr-S-C-O isotopic and microscopic analysis. Particularly, combined with the Ba isotope, the relationship between voluminous Ba precpitation and the paleoceanographic environment of the early Cambrian would be better constrained.