A “Facility-Exposure Matrix” (FEM) is proposed to assess exposure to chemical carcinogens and radionuclides in a cohort of nuclear workers. Exposures are to be attributed in the following way: a worker reports to an administrative unit and/or is monitored for exposure to ionising radiation in a specific workplace. These units are connected with a list of facilities for which exposure is assessed through a group of experts. The entire process of the FEM applied in one of the nuclear centres included in the study shows that the FEM is feasible: exposure durations as well as groups of correlated exposures are presented but have to be considered as possible rather than positive exposures. Considering the number of facilities to assess (330), ways to simplify the method are proposed: (i) the list of exposures will be restricted to 18 chemical products retained from an extensive bibliography study; (ii) for each of the following classes of facilities: nuclear reactors, fuel fabrication, high-activity laboratories and radiation chemistry, accelerators and irradiators, waste treatment, biology, reprocessing, fusion, occupational exposure will be deduced from the information already gathered by the initial method. Besides taking into account confusion factors in the low doses epidemiological study of nuclear workers, the matrix should help in the assessment of internal contamination and chemical exposures in the nuclear industry.