The diversity and distribution of methanogenic archaea in a four-compartment anaerobic baffled reactor (ABR) treating sugar refinery wastewater were investigated by polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE). At an organic loading rate of 5.33 kg COD/m3·day, the ABR could perform steadily with the mean chemical oxygen demand (COD) removal of 94.8% and the specific CH4 yield of 0.21 l/g CODremoved. The CH4 content in the biogas was increased along the compartments, whereas the percentage of H2 was decreased, indicating the distribution characteristics of the methanogens occurred longitudinally down the ABR. A high phylogenetic and ecological diversity of methanogens was found in the ABR, and all the detected methanogens were classified into six groups, including Methanomicrobiales, Methanosarcinales, Methanobacteriales, Crenarchaeota, Arc I, and Unidentified. Among the methanogenic population, the acid-tolerant hydrogenotrophic methanogens including Methanoregula and Methanosphaerula dominated the first two compartments. In the last two compartments, the dominant methanogenic population was Methanosaeta, which was the major acetate oxidizer under methanogenic conditions and could promote the formation of granular sludge. The distribution of the hydrogenotrophic (acid-tolerant) and acetotrophic methanogens in sequence along the compartments allowed the ABR to perform more efficiently and steadily.