Trace elements of bronze vessels, which are from Zongyang County, Anhui Province and dated from the Western Zhou Dynasty to Warring States Period, and copper prills in the slag from Tangjiadun Site, were analyzed with LA-ICP-MS to determine their copper ores sources. Results show that contents of elements Co, As, Sb, Ag and Bi, et al. in the copper prills of slags from Tangjiadun site are high, which are different from the elements characteristics of smelted copper metal from Tongling and Tonglvshan site of mining and smelting. Copper ores sources of the bronze vessels from Zongyang County are stable from the Western Zhou Dynasty to Warring States Period. The copper ores mainly come from the vicinity around Tangjiadun site in Zongyang County and a small proportion is from Tongling area in the south of the Yangtze River. It is feasible that LA-ICP-MS can be used to determine trace elements in the ancient bronze vessel and copper prills in the slag from the site of mining and smelting, which provides a in situ nondestructive analysis technology for bronze vessel analysis and has important potential applications in the study on copper ores sources of ancient bronze vessels.