Environmental exposures throughout the life of the subjects (exposome) could have a negative effect on their health outcomes. From this perspective, analysis of volatile organic compounds (VOCs) in human exhaled breath is emerging as a non-invasive tool to identify and check exposure to harmful agents. Breath analysis is also a helpful technique for human metabolism assessment, which allows for examining the impact of environmental exposures on organisms (biomonitoring). In this paper, a comprehensive review has been carried out to assess the use of breath analysis by mass spectrometry-based technologies for monitoring environmental exposures. Records of the last 20 years from three databases (PubMed/Medline, Scopus, and Web of Science) have been evaluated independently by two reviewers. A total of 38 studies fulfilled the criteria for eligibility. It has been compiled information about environmental exposures that have been monitored by breath analysis using mass spectrometry-based analytical platforms, as well as the most commonly used protocols of breath sampling, analytical techniques, and statistical methods. In addition, special emphasis has been placed on the huge range of VOCs selected as potential markers of environmental exposures. Despite the potential of breath analysis for monitoring human exposure, further research is needed to identify useful markers to establish it as a routine tool.