The purpose of the study is to analyze the possibility to identify the pollution genesis of the underground hydrosphere based on the data on polyarenes as geochemical markers. Their marker role is due to their toxicity, persistence and confinement to specific pollution sources and natural and technogenic processes. The main research method is the analysis of indicator ratios of polyarenes. The object of research is groundwater from different regions of the world, which are polluted by natural and anthropogenic polyarenes. The main directions of domestic and foreign researches as well as the problems of their implementation are shown. The use of indicator ratios enabled successful identification of pyro- and petrogenically polluted samples of groundwater also the examples of the study of polyarenes as geochemical markers were demonstrated. The polyarenes are shown to be an effective indicator of the pollution genesis in the underground hydrosphere. However, their analysis requires the use of modern methods of sampling, sample preparation and extraction, which significantly complicates research in practice.