In this study, the composition of tars collected during a six-day underground coal gasification (UCG) test at the experimental mine ‘Barbara’ in Poland in 2013 was examined. During the test, tar samples were taken every day from the liquid product separator and analysed by the methods used for testing properties of typical coke oven (coal) tar. The obtained results were compared with each other and with the data for coal tar. As gasification progressed, a decreasing trend in the water content and an increasing trend in the ash content were observed. The tars tested were characterized by large changes in the residue after coking and content of parts insoluble in toluene and by smaller fluctuations in the content of parts insoluble in quinoline. All tested samples were characterized by very high distillation losses, while for samples starting from the third day of gasification, a clear decrease in losses was visible. A chromatographic analysis showed that there were no major differences in composition between the tested tars and that none of the tar had a dominant component such as naphthalene in coal tar. The content of polycyclic aromatic hydrocarbons (PAHs) in UCG tars is several times lower than that in coal tar. No light monoaromatic hydrocarbons (benzene, toluene, ethylbenzene and xylenes—BTEX) were found in the analysed tars, which results from the fact that these compounds, due to their high volatility, did not separate from the process gas in the liquid product separator.