To understand the role of functional groups in the spontaneous combustion of lignite coal, the distribution of functional groups in the lignite coal of the Sajau Formation in the Berau Basin, Indonesia, was studied. The functional group characterization was carried out using the Fourier Transform Infra Red (FTIR) method. The results revealed the presence of four functional groups, namely hydroxyl structures, aliphatic structures, oxygen-containing structures, and aromatic structures. The lignite contained more hydroxyl and oxygen-bearing functional groups, from which aliphatic and aromatic; therefore, spontaneous combustion becomes easy in lignite coal.