Analytical tests to measure chemicals in saliva can be employed for numerous analytes, endogenous compounds or xenobiotics. The objective was to determine which chemicals can be analysed with this matrix, which analytical methods are applicable, and what application is possible for biomonitoring. We reviewed the literature using three databases, MEDLINE, PubMed and Scopus, collecting articles on different kinds of analysis in saliva. Studies were principally about molecules of clinical interest, xenobiotics, especially drugs of abuse, and chemicals used at workplaces; some substances show no relevant correlation with exposure data while others seems to be of particular interest for systematic use for biomonitoring. Currently, saliva is used far less than other biological fluids but its use for biomonitoring of exposure to chemicals might open up new areas for research and would certainly simplify the collection of biological samples.