Tar remaining in the gasification cavity during underground coal gasification (UCG) is an important pollution source, while the reported studies only focus on the tar behavior at the outlet. The present work aims to compare the tar properties from the reaction zone and the outlet, analyze the tar evolution during gasification, and discuss possible measures to control tar pollution. Tar was sampled with a self-developed equipment from an ex-situ underground coal gasification experimental system and analyzed by GC-MS. The gas composition, temperature, and PM10 were also compared for the reaction zone and the outlet. Compared with the tar from reaction zone, the tar from outlet has a smaller percentage of high boiling point content, PAHs, C, O, N, S, Cl, Si, and a larger percentage of H. The PAHs percentage in tar at the outlet in this work is closer to the field data than the lab data from literature, indicating the experimental system gives a good simulation of tar behavior in underground coal gasification. Condensation due to a fast temperature drop is one of the main reasons for PAHs decreasing. Tar cracking and soot formation also cause the decrease of heavy tar, proven by the light gas and particulate matter results.