Hexavalent chromium (Cr(VI)) compounds have been classified as carcinogenic to humans. This study evaluates the extent and magnitude of occupational exposures to Cr(VI) in Italy. Data were collected from exposure registries of companies compulsorily notified by the National Workers' Compensation Authority. Each measurement was characterized by economic activity sector, work force size, worker personal data, job description, year of measurement, and level of exposure. Descriptive statistical analysis was carried out on the retrieved information. The number of workers potentially exposed was estimated for some industrial sectors. A mixed-effects model was adopted to evaluate the association between exposure variables and exposure concentrations. Over 8400 measurements of Cr(VI) exposures were selected from the database of registries for 1996-2009. Most exposures occurred in the manufacture of fabricated metal products (>50%), and the occupational group most frequently measured was metal finishing-, plating- and coating-machine operators (>52%). Measurements were associated with various Cr(VI) compounds, including chromium trioxide, potassium dichromate, sodium dichromate, strontium chromate, and zinc chromate. Cr(VI) exposure has decreased in more recent years, and the fixed-effects (Cr(VI) compound, activity sector, size and location of the facility, job category, and year of measurement of the final statistical model explained more than 70% of the variance in the observed exposure data. This study summarized data recorded in the Italian occupational exposure database and identified specific exposure patterns to Cr(VI). The mean level of exposure to Cr(VI) was 30.41 μg/m³, and 50,118 workers were estimated at exposure risk in the selected industrial sectors. Systematic recording of occupational exposures is a source of data that allows recognition of high risk situations and improvements in exposure assessment for epidemiologic studies.