The furnace walls and slags from Tangjiadun site in Zongyang County of Anhui Province were analyzed by means of X-ray fluorescence spectrometer (XRF), X-ray diffraction analyzer (XRD), scanning electron microscope (SEM) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) in order to probe into the copper smelting technology of Tangjiadun site. Results show that the furnace walls are from the copper smelting furnaces and the slags are the reduced slag. According to the concentrations of elements As, Ag, Sb and Bi in copper prills, it can be calculated that relative probabilities that these copper prills in the slags come from the copper sulfide ore reach over 87. 87%. Combined with the results of SEM-EDS, the smelting process of “copper sulphide ore-copper” was used in Tangjiadun site, and the smelting remains (slags and prills) were considered as the smelting products of sulphide copper ore. This study is not only beneficial to research on bronze cultural of Zongyang County, but also has very important significance to explore the development and evolution of bronze metallurgy technology in Zongyang-Lujiang area.