The barite deposits hosted in Early Cambrian black shales in South China is one of the representative world famous sediment hosted stratiform deposits. This paper reports the discovery of zoned hyalophane for the first time, based on a case study in the Dahebian barite deposits, Tianzhu county, South China. Analytical results of electron microprobe analysis show that outer BaO content is 1653% to 1786% and K2O content is 777% to 819%, while BaO content is 1204% to 1421% and K2O content is from 860% to 979% in the core. Combined with the geological setting and previous research results, we addressed geological implications of this discovery. It supports the impact of hydrothermal liquid in the formation of the barite deposit. Multiple stages of barium rich fluid participated in the barite formation, and the mineralization was fault controlled, episodic and progressive. This not only further implies the hydrothermal sedimentary genesis of the deposit, but also betters the understanding of mineralization process. These results may have general implications to the other studies worldwide, as the Dahebian deposit is the biggest in volume of such deposits in the world.