Abstract: Coal fires are a global ecological disaster, leading not only to the loss of coal resources but also to the release of large amounts of organic pollutants such as polycyclic aromatic hydrocarbons (PAHs), threatening regional ecological security. In the Zhundong coalfield, 28 soil samples from six fire zones are collected. These samples are systematically analyzed for the pollution characteristics, compositional patterns, and toxic ecological risks of 16 priority-controlled PAHs. The results show that significant gradient variations in PAH pollution levels are observed among the three types of fire zones. In the re-ignited fire zones, the total concentration of PAHs ranges from 180 to 203 219 µg/kg, with low- and medium-ring components being dominant. However, a simultaneous enhancement of high-ring PAHs (e.g., BaP, DahA) is observed in a few samples, leading to an order-of-magnitude increase in toxic equivalency. In the untreated fire zones, w(ΣPAHs) ranges from 1 055 to 28 204 µg/kg, indicating a high pollution background. Localized enrichment of high-ring PAHs is found in areas such as fracture zones and gas venting points, resulting in significantly higher ecological risks than those in surrounding areas. In the treated fire zones, w(ΣPAHs) is reduced to 395 µg/kg, indicating a substantial decrease in pollution load, although small amounts of highly toxic monomers (e.g., BaP) remain. Analysis of pollution sources reveals that the w(Fla)/w(Fla+Pyr) ratio consistently indicates a combustion source, suggesting that PAHs in the fire zones mainly originate from coal/biomass combustion. The generally low w(Ant)/w(Ant+Phe) ratio is attributed to the influence of volatilization–migration–condensation deposition processes on tar. The ecological risk assessment shows that the overall ecological risk of PAHs in coalfield fire zone soils is relatively high. Among them, the risks in re-ignited and untreated fire zones are particularly severe, while treated fire zones still exhibit long-term residual risks. The toxic equivalency analysis indicates that low- and medium-ring components form the baseline toxicity, while local enhancement of highly toxic high-ring PAHs leads to increased toxicity in certain samples. A differentiated management approach guided by classification is proposed: in re-ignited fire zones, focus is placed on source control and localized deep removal, using technologies such as geological sealing and microwave-assisted pyrolysis to inhibit secondary PAHs release. In untreated fire zones, fire control and re-ignition prevention are prioritized, and remediation techniques such as biochar application are integrated during coal fire treatment to reduce the overall soil pollution level. For treated fire zones, long-term monitoring and ecological restoration are emphasized to continuously reduce residual toxicity risks. These findings provide scientific evidence and technical support for organic pollution risk control and ecological restoration in coalfield fire zones.