The National Human Exposure Assessment Survey (NHEXAS) Phase I field study conducted in EPA Region 5 provides extensive exposure data on approximately 250 study participants selected via probability sampling. Associated environmental media and biomarker (blood, urine) concentration data were also obtained to aid in the understanding of relationships of the exposures to both contaminant sources and doses. Distributional parameters for arsenic (As), lead (Pb), and four volatile organic compounds (VOCs)—benzene, chloroform, tetrachloroethylene, and trichloroethylene—were estimated for each of the relevant media using weighted data analysis techniques. Inter-media associations were investigated through correlation analysis, and longitudinal correlations and models were used to investigate longitudinal patterns. Solid food appeared to be a major contributor to urine As levels, while Pb levels in household (HH) dust, personal air, and beverages all were significantly associated with blood Pb levels. Relatively high (>0.50) longitudinal correlations were observed for tap water Pb and As, as compared to only moderate longitudinal correlations for the personal air VOCs.