The nature of the association or interaction between organic matter (OM) and inorganic minerals (IM) in oil shale has not been well characterized yet, which is fundamental to all proposed separation and oil recovery procedures. In this work, we found that supercritical ethanolysis (SE) and stepwise acid treatment could be used to reveal the relationship between OM and IM in Huadian oil shale. The acid treatment destroyed the complex and strong interaction between OM and IM, thus leaving OM as a free state. Fortunately, OM was able to be partially degraded into small molecules by SE through breaking weak bonds. Extractable OM of 36.1% exists in oil shale as a free state; 28.8, 20.8, and 14.3% of extractable OM have chemical bonds with carbonate, pyrite, and silicates, respectively. Detailed information of the chemical compositions of OM was obtained, based on which the interaction types between IM and OM were also concluded. The interaction of OM with IM depends on the species of minerals. Carbonates of minerals in the oil shale have a strong chemical interaction with carboxylic acids of OM via carbonating. There are strong bonding interactions between pyrite and alkanoic acids of OM via -COO-. Si-containing compounds with Si-O ether bonds and a large number of alcohols and ethers, as well as fatty acids, were detected in the ethanolysis products after washing out silicates. It is reasonably speculated that these organic compounds mainly exist via forming Si-O ethers with silicates in the oil shale.