Biogenic CBM is an important component of detected CBM, which is formed by coal biodegradation and can be regenerated by anaerobic microorganisms. One of the rate-limiting factors for microbial degradation is the bioavailability of coal molecules, especially for anthracite which is more condense and has higher aromaticity compared with low-rank coal. In this paper, NaOH solution with different concentrations and treating time was employed to pretreat anthracite from Qinshui Basin to alter the coal structure and facilitate the biodegradation. The results showed that the optimal pretreatment conditions were 1.5 M NaOH treating for 12 h, under which the biomethane production was increased by 17.65% compared with untreated coal. The results of FTIR and XRD showed that NaOH pretreatment mainly reduced the multi-substituted aromatics, increased the CO in alcohols and aromatic ethers and the branching degree of aliphatic chain, and decreased the aromatic ring structure, resulting in the improvement of coal bioavailability and enhancement of biomethane yield. And some organics with potential to generate methane were released to filtrate as revealed by GC-MS. Our results suggested that NaOH was an effective solution for pretreating coal to enhance biogenic methane production, and anthracite after treating with NaOH could be the better substrate for methanogenesis.