The mineralogy of the Early Cambrian Ni-Mo polymetallic black shale ores at the Sancha deposit, South China, was investigated to better the understanding of the complex ore genesis by optical microscope, electron microprobe, and scanning electron microscope. Analytical results show that the sulfides in the ore bed mainly comprise C/MoS2 mixed-layer phase (MoSC), millerite, and pyrite. Of these, MoSC and millerite are the main ore minerals of Mo and Ni, respectively. Pyrite is subdivided into six types based on its morphology, occurrence, relationship to Ni-and Mo-bearing minerals, and chemical composition. Many millerite crystals cut early-formed MoSC, implying that these two minerals formed at different stages. The concentrations of biogenic elements (e.g., Sb) in the MoSC are high compared with those in millerite, implying a close relationship between MoSC and organic matter. These data provide a new and improved understanding of the complex ore genesis at the Sancha deposit, and can be applied to other black-shale-hosted mineral deposits worldwide.