Oxidative potential (OP) is considered to be an efficient indicator of particulate matter (PM) to induce oxidative stress in the lungs and is increasingly considered to be a relevant health metric. In this study, two complementary OP assays were deployed, including dithiothreitol (DTT) and ascorbic acid (AA) assays, to investigate the potential toxicity (as generators of oxidative stress) of respirable fractions (DD4, < 4 μm) of deposited dust (DD500, < 500 μm) in underground low-S and low-pyrite coal mines in Henan Province, Central China. The OP^DTT of DD4 is higher than that reported for other types of atmospheric PM, whereas the OP^AA of DD4 is similar and/or slightly higher. Cross-correlation and multilinear regression analyses are applied using datasets of major mineral and geochemical patterns in the DD4 samples and the respective OP values to identify the major drivers for OP in respirable coal dust. Thereafter, the patterns of DD4 are compared with those of DD500 and the parent coals to determine the sources of OP-relevant substances. OP^DTT is mainly governed by some trace elements (Sb, As, Li, B, Sr, and Pb) and minor minerals (anatase, quartz, siderite), and their synergistic effect may be one of the reasons for the high DTT consumption. For OP^AA, quartz, total clay (sum of illite, kaolinite, tobelite, and clinochlore) and Ni, Cr, Co, Si, and S, play an important role in regulating the OP^AA of pyrite-free DD4 samples. These OP-relevant substances have three sources: coal dust, which has a similar composition in DD4, DD500, and the parent coal (such as siderite and its associated elements); gangue dust, which does not occur in the parent coal but is widely detected in DD4 and DD500 (such as quartz, kaolinite, and relevant elements); and cement dust (from gunite galleries), which is mainly calcite- and calcite-associated elements.