The study aims to investigate the variation of the coal dielectric properties during coal low-temperature oxidation and the effect of oxidation product on the coal dielectric properties. Four different types of coal were prepared under low-temperature oxidation condition, and the coal dielectric properties were measured with an impedance analyzer at frequencies ranging between 20 Hz and 30 MHz. The oxygen-containing functional groups in oxidized coal samples were semi-quantitatively evaluated using Fourier transform infrared spectroscopy. Low-temperature oxidation stage of coal spontaneous combustion could be predicted according to the change of coal dielectric properties in the process of temperature rise. It was found that the dielectric constant of coal with high water content decreased exponentially with temperature. For coal sample with low water content, the dielectric properties changed piecewise linearly with temperature. Coal dehydration was considered to be the reason for the decrease of the dielectric constant from 30 °C to 120 °C. The increase of the relative content of oxygen-containing functional groups, especially carbonyl compounds, could be the reason for the rise of the coal dielectric constant from T2 to T3.