Organochlorine pesticides and polychlorinated biphenyls (PCBs) are synthetic chemicals that are highly resistant to biodegradation and have proven adverse health effects. The objectives of this study were to determine concentrations of three selected organochlorine pesticides (p,p′-DDT, p,p′-DDE, HCB) and three specific PCB congeners (PCB 138, 153, 180) in adipose tissue and serum samples from an urban adult population (n=112) in the city of Santa Cruz de la Sierra, Bolivia, and to investigate their relationships within and between the two matrices and with selected socio-demographic characteristics. The percentages of samples positive for these compounds ranged from 40% for PCB 180 to 100% for p,p′-DDE in adipose tissue, and from 21% for HCB to 93% for p,p′-DDE in serum. Median number of residues per sample was five for adipose tissue and three for serum. Geometric mean concentrations indicate a considerable historical and recent exposure to organochlorine pesticides and PCBs in this population. Adipose tissue:serum ratios ranged from 149.3 to 590.3 (wet basis) and from 0.9 to 3.5 (lipid basis). We found positive and statistically significant correlations between adipose tissue and serum concentrations only in p,p′-DDE and HCB. This novel study in Bolivia underlines the need for human biomonitoring to assess exposure to environmental pollutants in South America.