Subaerial volcanism and atmospheric volcanic ash deposition have been recognized as factors that can greatly affect the nutrient content of the surface ocean and the redox conditions of the water column. Black siliceous, organic-rich mudstone and shale containing numerous volcanic ash layers were deposited in the South China Block during the Ordovician-Silurian transition. Although this association has been observed in other regions, whether there is a relationship between volcanic ash and the organic carbon contents and the effect of volcanic ash remains unclear. Based on analysis of the concentrations of major elements, trace elements, and total organic carbon in the volcanic ash and shale, we found that anoxic and high-productivity environments existed during the Ordovician-Silurian transition and that organic matter was preferentially preserved under these conditions. For the volcanic ash, we quantitatively estimated the depletion of the nutrient elements Fe, Si, and P (in percentages). The calculated results show that leaching removed 25–75% of the Fe, Si, and P in most of the ash samples in the study area, potentially leading to high marine primary productivity in the surface water. Redox conditions also played a major role in the preservation of organic matter. The trace element analysis results show that although productivity was high during the Ordovician-Silurian transition, organic matter was preferentially preserved in the Lower Silurian strata. Therefore, high organic matter flux and good preservation conditions both contributed to the formation of the organic-rich shale, and volcanic ash was the dominant source of nutrients for primary productivity.