Humans are widely exposed to chemicals. Today, there is an increased acknowledgement of the importance of measuring human and environmental exposures to man-made or refined chemicals. Different approaches have been applied over time, but during the past 25 years, there has been a general trend towards the use of human biomonitoring. A few studies have used human biomonitoring methodology to track contact allergens together with information on patch test reactivity. Hypothetically, the internal load of reactive chemicals might modify the immune response to haptens and the propensity to sensitize and elicit allergic contact dermatitis or develop tolerance. This review offers a general overview of human biomonitoring, including information about its typical application and methodology. Furthermore, studies that have attempted to perform simultaneous biomonitoring and patch testing are reviewed. It is concluded that all studies conducted until the present have focused on one or two routes of exposure (typically skin and oral exposure, but also skin and airway exposure), whereas no studies have investigated all routes at the same time. Also, there is a need for prospective studies, as all epidemiological studies so far have been cross-sectional.