In order to study the effect of inherent metals in coal on spontaneous combustion, Hongmiao lignite and Hongqingliang long-flame coal were demineralized by hydrochloric acid, the raw coal and demineralized coal were characterized by Fourier transform infrared spectrometry, X-ray diffraction, and synchronous thermal analysis experiments, and the corresponding ash content was detected by inductively coupled plasma mass spectrometry. The results show that the effect of demineralization on the volatile matter of low-rank coal is small, and the change of crystallite structure is not significant. The removed parts are mainly water-soluble salts and soluble minerals, such as carbonates and metal ions, that are not tightly bound to the organic matter of coal structure. The removed metal elements are mainly alkali metals Na and K, alkaline earth metals Ca, Mg, Sr, and Ba, and transition metals Fe, Mn, Ti, and so forth. The temperatures corresponding to the end of weight loss, ignition, and maximum weight loss rates were elevated on the thermogravimetric curves of the demineralized coal samples. The heat absorbed by evaporation of water in coal and the heat released by oxidation and combustion of coal are decreased to different degrees, indicating that the spontaneous combustion tendency of coal after demineralization is reduced, and alkali metal, alkaline earth metals, and transition metals in coal have a catalytic effect on spontaneous combustion of coal. After adding the metal chelating agent ethylenediaminetetraacetic acid (EDTA), the apparent activation energy decreased by 33.08 and 2.42%, respectively. EDTA and the alkali metal, alkaline earth metal, or transition-metal ions formed a stable chelate in coal. The catalytic activity of metals is weakened or even lost, thereby inhibiting spontaneous combustion of coal, and verifying the catalytic effect of internal metals in coal on the spontaneous combustion of coal.