The Punchuncaví Valley is one of the most polluted areas in central Chile affected by anthropogenic emissions from the Ventanas Industrial Complex (IC) where the most important industry is the copper smelter and refinery. In this context, this research aims were to assess the usefulness of the Cupressus macrocarpa as a biomonitor. The leaf samples were taken from five selected sites, located between 0.8 and 15 km away from the source. A total of 34 elements were analyzed in leaf samples by ICP-MS and examined by enrichment factor (EF), hierarchical cluster analysis (HCA), and principal component analysis (PCA). Leaf concentration of As, Ca, Cd, Cu, Dy, Er, Gd, K, Li, Mg, Mn, Mo, Na, Nd, P, Pb, Pr, S, Sb, Sr, Ti, Yb and Zn showed statistically significant differences between sampling sites (p-value < 0.05). A clear trend to increase the concentration of Cu, Sb, S, As, Cd and Pb with the proximity to the IC. Besides, high values of Cu (93.4–369 mg kg−1) and As (7.6–12.7 mg kg−1) were observed near to industrial area exceed the phytotoxic levels reported in plants with EF > 3000% for Cu and >1300% for As. The application of PCA and HCA identified 6 factors related to the industrial complex, traffic and geogenic sources, providing the greatest variance the component related to industrial activity mainly with copper smelter and refinery. According to the results, the C. macrocarpa leaves are a good biomonitor to evaluate the high pollution load for anthropogenic elements in industrial areas.