AbstractThe biomarker analysis of benzene, toluene, ethylbenzene and xylene (BTEXs) in biological samples is the primary technique for evaluating these compounds in occupational and environmental exposures. The BTEX biomarkers are widely used to study the BTEX distribution in the environment and workplaces. Liquid–liquid extraction and solid‐phase liquid extraction are among the most commonly used conventional methods to analyze biological indices of BTEXs. New methods have been proposed to analyze BTEX biomarkers using novel adsorbents such as sol–gel composite nanotubes, molecularly imprinted polymers and metal–organic frameworks, which are based on the application of needle trap devices, microextraction by packed sorbent, and solid‐phase microextraction techniques. This paper provides an overview of new methods since 2015 regarding applying microextraction methods based on new adsorbents and analyzing BTEX biomarker compounds for occupational and environmental exposures. The results were compared with the liquid‐phase microextraction methods recommended for urinary BTEX biomarkers.