This experimental study aims to characterize the bioavailability of six Surat Basin Walloon coals to exogenous methanogenic consortia, and the possible compositional and environmental factors that control bioavailability. Finely crushed coal cores samples were inoculated with digested sludge culture sourced from domestic wastewater treatment plants in biomethane potential bottles (BMP bottles) maintained at mesophilic temperature. Degradation of coal compounds was demonstrated via GC-MS characterization of methanol and dichloromethane (DCM) extracts of coals, as well as analysis of volatile fatty acids and alcohols and total dissolved organic carbon (TOC) in water eluents of coals conducted before and after biodegradation. The resulting methane yields ranged from 14 to 33 μmol/g, with an average of 21 μmol/g (0.515 m3/t) achieved within 30 days. Organic solvent-extractable materials accounted for 3.8 to 12% of coal weight. Aliphatic compounds, primarily medium-long-chain n-alkanes, n-alcohols and esters dominated the solvent extracts. Aromatics were detected up to three fused rings, and are rich in dibenzofuran, alkyl benzene, alkyl polyaromatic hydrocarbons, and acetyl diphenyl. The abundance of solvent-extractable matter was found to rely on liptinite content, particularly suberinite. Preservation of these compounds was thought to be facilitated by vitrinite, such as telinite and collotelinite that are rich in micropores, serving as storage for the hydrocarbons. On the other hand, environmental factors, such as microbes-carrying groundwater might compromise coal extractability by converting coal hydrocarbons to biogas. The study has revealed three levels of dependence regarding coal bioavailability: 1) Water solubility - An average 98% of aqueous compounds (based on TOC) was eliminated via biodegradation. These were mainly volatile fatty acids and alcohols, and to a lesser degree, medium-chain n-alcohols, esters and aliphatic amine; 2) Solvent extractability – approximately 35% of solvent-extractable compounds were biodegraded on average, with aliphatics being more bioavailable than aromatics; 3) Heterogeneous moieties, particularly aliphatic hydroxyl, ester bond, ether bond and C-N bond in aliphatic amine - These functional groups are characteristics of compounds that were heavily degraded. The study is to our knowledge, the first coal bioavailability research that demonstrated a detailed linkage between biomethane generation and bio-elimination of coal extractable compounds with connections to petrographic composition and possible environmental factors.