The rapid pyrolysis behavior of a kind of Indonesian oil sand was studied by a fixed-bed reactor. According to X-ray photoelectron spectroscopy (XPS), 1H nuclear magnetic resonance spectra (1H NMR) analysis, the organic structure model of oil sand and the occurrence of heteroatoms were proposed. Liquid products were characterized by gas chromatograph with mass spectrometer (GC-MS) and atomic emission detector for gas chromatography (GC-AED). In addition, the distribution of the gaseous product was analyzed using gas chromatograph (GC). During the rapid pyrolysis process, the tar yield reached its maximum at 450 °C, and the gas yield increased rapidly with the increasing temperature, while the residual sand yield displayed the opposite trend. Aromatic esters and aliphatic hydrocarbons were the predominant components of liquid products after rapid pyrolysis treatment. More stable heteroatom compounds, such as thiophene and furan, would be released into liquid product with an elevated pyrolysis temperature. Atoms like sulphur and oxygen on the aliphatic side chain were easily transformed into gaseous products such as H2S, CO2 and CO. Sulfur-containing compounds in oil sand minerals converted from sulfate to metal sulfide during the pyrolysis process. After thermal decomposition, heteroatoms compounds in organic matter transferred to gaseous product or liquid product along with the volatiles. However, heteroatom compounds in inorganic substances presented in residual sand in a more stable form.