Typically, the availability of appropriate data to estimate human exposures to toxic chemicals is scarce. Consequently, exposure assessments are often based on indirect surrogates of exposure, such as a combination of questionnaire data on time-activities and concentrations of toxic chemicals measured in environmental media (e.g., air, water, food, soil, dust). Recent advances, however, make it technically feasible and relatively affordable to measure low levels of multiple toxic chemicals in accessible human tissues (e.g., blood, urine). The increasing availability of biological markers for exposure, along with improvements in pharmacokinetic understanding, present new opportunities to estimate exposure from human tissue measurements and from knowledge of intake and uptake parameters. Biological monitoring provides exposure information that is usually complementary to the type of exposure information obtained from environmental monitoring. Biological and environmental monitoring can be used separately or together in order to meet desired objectives. We present here a discussion of the value of biological monitoring for improving exposure assessment. We emphasize the role of biological monitoring in identifying high-priority exposures, evaluating the effectiveness of intervention and prevention efforts, identifying at-risk subpopulations, recognizing time trends in population exposures, establishing reference ranges of tissue concentrations, and providing integrated dose measurements.