Occupational exposure to hexavalent chromium (Cr(VI)) can cause serious adverse health effects such as lung cancer and irritation of the skin and airways. Although assessment of chromium (Cr) in urine is not specific for Cr(VI) exposure, the total amount of Cr in urine is the most used marker of exposure for biomonitoring of Cr(VI). The purpose of this systematic review was fourfold: (1) to assess current and recent biomonitoring levels in subjects occupationally exposed to Cr(VI), with a focus on urinary Cr levels at the end of a working week, (2) to identify variables influencing these biomonitoring levels, (3) to identify how urinary Cr levels correlate with other Cr(VI) exposure markers and (4) to identify gaps in the current research. To address these purposes, unpublished and published biomonitoring data were consulted: (i) unpublished biomonitoring data comprised urinary Cr levels (n = 3799) of workers from different industries in Belgium collected during 1998-2018, in combination with expert scores indicating jobs with Cr exposure and (ii) published biomonitoring data was extracted by conducting a systematic literature review. A linear mixed effect model was applied on the unpublished biomonitoring data, showing a decreasing time trend of 30% in urinary Cr levels. Considering the observed decreasing time trend, only articles published between January 1, 2010 and September 30, 2020 were included in the systematic literature search to assess current and recent biomonitoring levels. Twenty-five studies focusing on human biomonitoring of exposure to Cr(VI) in occupational settings were included. Overall, the results showed a decreasing time trend in urinary Cr levels and the need for more specific Cr(VI) biomarkers. Furthermore, this review indicated the importance of improved working conditions, efficient use of personal protective equipment, better exposure control and increased risk awareness to reduce Cr levels in biological matrices. Further investigation of the contribution of the different exposure routes is needed, so that better guidance on the use of control measures can be provided. In addition, this review support the call for more harmonization of human biomonitoring.