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Methane (CH4) emissions from sewage sludge composting can be reduced by using biochar more effectively. This study investigates the impact of different structure of biochar on CH4 emissions during sewage sludge composting. Corncob biochar (CB, pore size = 35.3990 nm), rice husk biochar (RB, pore size = 3.4242 nm) and wood biochar (WB, pore size = 1.6691 nm) were applied to the composting. The results showed that biochar decreased CH4 emissions, mainly through the indirect effect of improving the pile environment. Compared with the control group (CK), the biochars with smaller pore structures, WB and RB, reduced CH4 emissions by 41.83% and 33.59%, respectively, compared to only 8.20% for CB, which has a larger pore structure. In addition, RB and WB increased the free air space (FAS) by more than 10% and CB improved the microbial diversity. Methanothermobacter was reported in WB and RB, with an abundance of 45.45% in WB. Redundancy analysis (RDA) showed that pore size was positively correlated with the CH4 emission rate. The results of this study can provide a theoretical reference for CH4 reduction from biochar co-composting of sewage sludge.