The increasing population in urban areas in the last decades requires an effort to understand the geochemistry of contaminant elements in urban soil. Topsoil plays a crucial role in the exposure of Potentially Toxic Elements (PTEs) to humans through ingestion, dermal contact, and inhalation. In Chile, the last census revealed that 88.6% of people live in cities or towns and only 11.4% in rural areas. This study presents the first systematic geochemical survey of urban soil in the city of Valdivia, in the South of Chile. Topsoil samples (0-10 cm depth) were collected in less disturbed locations within the city at 130 sampling sites using a grid of 0.25 km(2) squares covering a total area of approximately 30 km(2). The concentrations of Al, Fe, Na, Ca, Mg, K, Ti, Be, V, Cr, Mn, Co, Ni, Cu, Zn, As, Mo, Sn, Cd, Se, Pb and Hg were measured. The results showed that high concentrations of Cu, V, Zn and Pb are located mainly in the city's northern area and exceed international soil quality legislation for agricultural use. Data processing comprised plotting of individual spatial distribution maps and the use of a combination of multivariate statistical methods. Hierarchical cluster analysis and principal component analysis identified three element associations. The two element groups V-Al-Ti-Fe-Cr-Co-Mn-Be-Ni and Ca-Na-K-As-Mg are interpreted as a dominant lithological origin related to the most pristine soil conditions in less populated areas. By contrast, the Sn-Pb-Zn-Mo-(Cu-Hg) association presents a significant correlation with urbanization indicators, including vehicular traffic and industrial activities developed since the end of the nineteenth century in Valdivia.