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The high temperature in which sugarcane vinasse (SV) is generated (~ 90 °C) and the positive effect of higher temperatures in biochemical reactions have motivated the evaluation of SV anaerobic digestion (AD) under extreme temperature conditions. Two-stage (acidogenic/methanogenic) and single-stage (methanogenic) AD of SV were evaluated under 70 °C in structured-bed reactors. The extreme temperature was beneficial to the acidogenic step of the two-stage AD process. The methane production, however, was hindered at 70 °C. The VMP of the single and two-stage reactors accounted, respectively, for only 13% and 7% of the production rate reported in sugarcane vinasse AD at 55 °C. At 70 °C, the main genera responsible for methane production was Methanothermobacter and the acetoclastic methanogenesis did not occur, resulting in acetic acid build up (15,800 mg L−1). These results brought a new perspective for sugarcane vinasse management, with acetic acid production alternatively to methanization. In this perspective, two-stage process would be composed of acidogenic and acetogenic reactors, and beyond acetate, hydrogen and other soluble compounds could be recovered in a complete biorefinery process. [ABSTRACT FROM AUTHOR]