Addressing the environmental risks related to contamination of groundwater with the phenolics, benzene, toluene, ethyl benzene, xylene (BTEX) and polycyclic aromatic hydrocarbons (PAHs), which might be potentially released from the underground coal gasification (UCG) under adverse hydrogeological and/or operational conditions, is crucial in terms of wider implementation of the process. The aim of this study was to determine the main organic pollutants present in the process condensate generated during the UCG trial performed on hard coal seam in the Experimental Mine ‘Barbara’, Poland; 8,933 L of condensate was produced in 813 h of experiment duration (including 456 h of the post-process stage) with average phenolics, BTEX and PAH concentrations of 576,000, 42.3 and 1,400.5 μg/L, respectively. The Hierarchical Clustering Analysis was used to explore the differences and similarities between the samples. The sample collected during the first 48 h of the process duration was characterized by the lowest phenanthrene, anthracene, fluoranthene and pyrene contents, high xylene content and the highest concentrations of phenolics, benzene, toluene and ethyl benzene. The samples collected during the stable operation of the UCG process were characterized by higher concentrations of naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)anthracene, chrysene, while in the samples acquired in the post-process stage the lowest concentrations of benzene, toluene, naphthalene, acenaphthene and fluorene were observed.