The circadian time structure (CTS) has long been the subject of research in occupational medicine, but not to industrial toxicology, including methods of setting threshold limit values (TLVs) and employee biological monitoring. Numerous animal and human investigations document vulnerability to chemical, contagion, and other xenobiotics varies according to the circadian time of encounter. Permanent and rotating nightshift personnel are exposed to industrial contaminants in the same or higher concentration as dayshift personnel, and because of incomplete CTS adjustment to night work, contact with contaminants occurs during a different biological time than day workers. Thus, the amount of protection afforded by certain TLVs, especially for employees of high-risk settings who work night and other nonstandard shift schedules, might be inadequate. The CTS seems additionally germane to procedures of employee biological monitoring in that high-amplitude 24 h rhythms in biomarkers indicative of xenobiotic exposure may result in misjudgment of health risks when data are not gathered in sufficient frequency over time and properly interpreted. Biological reference values time-qualified for their rhythmic variation, currently of interest to laboratory medicine practice, are seemingly important to industrial medicine as circadian time and work-shift specific biological exposure indices to improve surveillance of personnel, particularly those working nonstandard shift schedules.