The Ni–Mo–PGE polymetallic layers, from Southern China (Huangjiawan mine, Zunyi region, northern part of the Guizhou Province), were analyzed by micro-PIXE. These samples are known to be enriched with acidic elements and basic elements. Some of them, like Ag, Au, Pt, Pd, Se and Mo, are of large economic value. The distributions of Fe, Mo, Ni, As, Se and Pd in black shales samples are studied. The correlation among those elements has also been investigated. Trace element data from minerals, the noble metals’ mode of occurrence and correlation with other elements are all significant in mineralogy. Such information can help in understanding the genesis of the deposit and also aid the exploration strategy.