Biochar can be used as a soil amendment. However, it generally possesses unique physicochemical properties and complex organics, which could affect soil methanogenesis. In this study，straw-based biochars obtained at 300 °C (BC300), 500 °C (BC500) and 700 °C (BC700) were added to the paddy soil. Compared with the blank group, BC300 significantly increased paddy soil methane emissions by about 38%. However, this promoting effect gradually disappeared with the increase of pyrolysis temperature, and the inhibition even appeared in the BC700 group with the methane reduction by 18.2%. This might be related to the organics released from biochar. Van Krevelen (VK) diagram showed that the aromaticity of BC700 and BC500 were significantly higher than BC300. Fluorescent analysis further revealed that BC300 increased the amount of degradable fluorescent organics in the soil, which could provide more substrate for methane production. Moreover, as pyrolysis temperature increased, the fluorescent organics released were more likely to be non-biodegradable humus. In addition, it was shown that BC700 could adsorb some inherent organics in the soil, and thus reduced the total organic content and inhibited soil methane emissions. Microbial analysis showed that methanogenesis had a positive correlation with the abundance of syntrophic bacteria (e.g. Desulfobacca and Clostridium) which had ability to further degrade various types of organics and provided substrates to the methanogens. This article provides a deeper understanding regarding for the effects of biochar on methane emission from paddy soil in terms of organics and microbial perspectives.