The study sets out to characterise the bioavailability of six Surat Basin Walloon coals from different stratigraphic layers in a single borehole to environmental methanogenic consortia. Factors that control bioavailability have also been investigated on grounds of coal petrographic composition and the organic composition of solvent-extractable matter. Finely crushed coal core samples were inoculated with digested sludge culture from domestic wastewater treatment in serum bottles kept anoxically before incubation at mesophilic temperature over 30 days for biomethane production. Degradation of coal compounds was demonstrated via GC-MS characterisation of methanol and dichloromethane (DCM) extracts, in combination with aqueous volatile fatty acids and alcohols and total organic carbon (TOC) analysis on fresh and microbially-digested coal samples. The resulting methane yields ranged from 14 to 33 mu mol/g, with an average of 21 mu mol/g (0.515 m(3)/t), comparable to those previously reported for subbituminous coals. Organic solvent-extractable materials that accounted for 3.8 to 12% of coal weight were generally dominated by aliphatic compounds, composed of mainly medium-long-chain n-alkanes, n-alcohols and esters. Aromatics were detected up to three fused rings, and are rich in dibenzofuran, alkyl benzene, diphenyls and alkyl PAH (polymeric aromatic hydrocarbon). The abundance of solvent-extractable matter was found to be positively associated with liptinite content, particularly suberinite, sporinite and liptodetrinite. Preservation of these compounds was thought to rely on vitrinite, such as telinite and collotelinite that are rich in micropores, serving as storage for the hydrocarbons. Environmental factors, such as microbe-carrying ground-water might compromise coal extractability by converting coal hydrocarbons to biogas. Bioavailability of coal was shown to be controlled by three factors: 1) Water solubility - Bioassay eliminated an average 98% of aqueous compounds (based on TOC), which were dominated by volatile fatty acids and alcohols, and to a lesser degree, medium-chain (primarily C-10 to C-20) n-alcohols, esters and aliphatic amine; 2) Solvent extractability - 34.5% of solvent-extractable compounds were shown to be biodegraded (based on peak intensity in GC-MS), with methanol extracts being more bioavailable than DCM's; 3) Heterogeneous moieties, particularly aliphatic hydroxyl group, ester bond, ether bond and C-N bond in aliphatic amine - These functional groups present heteroatoms that can lower the activation energy of nearby bonds, making them vulnerable for microbial cleavage. Compound degradation in bioassays was shown to be clearly associated with methane yield, but only a small proportion degraded was converted to methane. Further improvement may be achieved via proper adaptation of the current microbial community.