In-situ LA-ICP-MS and S isotopes of pyrite from the Baoshan Cu polymetallic deposit were conducted to investigate the ore-forming process and the enrichment mechanism of elements. Three generations of pyrite (Py I, Py II, and Py III) in the skarn-type ores and pyrite in the carbonate-hosted sulfide ores from central, western, and northern (C_Py, W_Py, and N_Py) mining districts are selected for comparison. Compared with Py I and Py III, the contents of most elements in Py II are apparently higher. The As and Se contents are high within a wide range and are decoupled in the growth band of the C_Py. The highest As, Se, and Pb contents were found in W_Py and N_Py. These results indicate the drastic changes in the temperature and fluid mixing during the mineralization. The occurrence of fluctuation and change in temperature and f(O₂) was triggered by intermittent pulses of magmatic-hydrothermal fluids, mixing with meteoric water, and water-rock interactions. The sulfur isotopes of all species of pyrite indicated the magmatic source. The change in the f(O₂) conditions caused slight differences in the sulfur isotope compositions. Consequently, a metallogenic model was proposed to explain the ore-forming processes.