Coal mining originates environmental impacts on soil and water bodies, including the leaching of Potentially Toxic Elements (PTEs) and Polycyclic Aromatic Hydrocarbons (PAHs) in mine waste piles. This research aims to identify and characterize changes induced by self-burning in Technosols from a coal mine waste pile by means of a comprehensive hydropedological assessment encompassing geochemical, mineralogical, and hydrological data, bearing in mind the potential leaching of PTEs and PAHs. The soil profile from two contiguous areas (an area with normal pedological evolution vs. an area affected by self-burning) was characterized in terms of morphological features. Each soil horizon was sampled and analyzed for geochemical and mineralogical characterization. The unsaturated hydraulic conductivity (Ki) was also measured in all soil horizons. Finally, the leaching potential of PTEs and PAHs in water was evaluated. Several changes induced by self-burning were identified in the studied Technosols: development of specific soil horizons; destruction of humified organic matter; contrasting geochemical composition, especially in the deeper horizons; mineralogical modifications, pointing to clay minerals with higher ion exchange capacity and higher specific surface by sulphates of lower structural order; diverse Ki values in the intermediate and lower part of the soil profile; and specific susceptibility to leaching of PTEs and PAHs. The research demonstrated that self-burning causes severe changes of hydropedological relevance, with influence on the leaching of PTEs and PAHs.