Anthropogenic activities increase the amount of potentially toxic elements (PTEs) in the environment and consequently affect the quality of soils and water resources. This study aimed to investigate the concentrations, spatial distribution, and sources of soil and sediment pollution at the watershed scale for the following PTEs: aluminum (Al), barium (Ba), cerium (Ce), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), lanthanum (La), manganese (Mn), neodymium (Nd), nickel (Ni), lead (Pb), praseodymium (Pr), scandium (Sc), samarium (Sm), thorium (Th), titanium (Ti), vanadium (V), yttrium (Y) and zinc (Zn). One hundred and eighty-eight composite samples collected from preserved Cerrado areas, channel banks, agricultural areas, pastures, and riverbed sediments were used. Environmental contamination was assessed using geochemical indices and ecological risk assessment. The concentration of these elements often followed the order of riverbed sediment > channel bank > pasture > agricultural areas. Based on the pollutant load index, riverbed sediments and channel banks were classified as polluted, acting as a source of PTEs. The Gurgueia watershed, Brazil, was classified as unpolluted to moderately polluted, with low to no enrichment by PTEs. These values serve as a basis for future monitoring of the impacts resulting from the advance of agricultural and industrial activities in the region.