Located in the Puchuncavi Valley (PV) in central Chile is one of the most important and oldest industrial complexes (ICs) in the country. The PV is affected by anthropogenic emissions from the IC where the most important industry is a copper smelter and refinery. In this context, this study assessed the profile, concentration, and enrichment factors of the trace elements, both in the soil and in Cupressus macrocarpa leaves from this high-pollution-load area. The soil and leaf samples were taken from five selected sites, located between 0.8 and 15 km away from the IC. A total of 24 elements were analyzed by ICP-MS and examined by enrichment factor (EF), and PCA source analysis. Leaf concentrations of Ba, Ca, Cd, Cu, K, and Sr showed statistically significant differences between sampling sites (p-value < 0.05). In soil, element concentrations of Al, As, Ba, Cr, Cu, K, Li Mg, Mn, Na, Ni, Pb, and Ti showed statistically significant differences between sampling sites (p-value < 0.05). The source analysis of EFs in the samples of both soil and leaves detected three and four factors, respectively, related mainly to the industrial complex's copper smelter and refinery, coal-fired power plants, and geogenic sources. According to the PCA, the leaf EFs of anthropogenic elements from copper smelting showed that La Greda (LG, site closest to the IC) was significantly enriched in the elements Cu, Zn, As, Mo, and Pb, while the EF in the soil from LG showed high enrichment in Cu and significant enrichment in Pb.