Tonstein layers are found worldwide in the Permo‐Carboniferous coal‐bearing strata. This study investigates the geochronology, mineralogy, and geochemistry of four tonstein samples from the Permo‐Carboniferous Benxi Formation, Ordos Basin, North China Craton (NCC). The typical features of the studied tonsteins include thin beds, lateral continuity, angular quartz grains, and euhedral zircons with similar U–Pb ages, indicating a significant pyroclastic origin. In addition, the tonstein samples have low TiO2/Al2O3 ratios (< 0.02) and rare earth elements and yttrium (REY) concentrations with obvious negative Eu anomalies, indicating that the tonsteins have a felsic magma origin. Moreover, compared with the mean composition of clay shale, the studied tonsteins are characterized by high concentrations of the elements Nb and Ta, which may affect the concentration of the corresponding elements in surrounding coal seams. The zircon U–Pb ages of the tonsteins (293.9–298.8 Ma) provide a precise chronological framework on the Benxi Formation in the Ordos Basin, constraining the Gzhelian‐Aselian stages. The tonsteins were probably sourced from arc volcanism along the western margin of the NCC during the Early Permian, implying that the Alxa Terrane had not amalgamated with the NCC at that time.