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The fabrication of cathodes with carbonized Agave tequilana bagasse for Li–S batteries is performed for the first time. Three porous carbonaceous structures are developed and studied to elucidate the best carbon textural properties in terms of their surface area and pore size distribution: hierarchical porosity, highly microporous, and nonporous material, for sulfur hosting in Li–S cathodes. N2 physorption, scanning electron microscopy, infrared spectroscopy, and potentiometric titrations analysis are performed to determine the textural, morphology, and physicochemical properties. The fabricated coin cells, CR2032, with cathodes made of mesoporous carbons, display a high discharge current (≈1600 mAh g−1), superior performance, and cyclability up to 250 cycles. The performance of batteries is found to be strongly influenced by surface area and pore size of the carbon materials. The carbonized tequila bagasse hosting sulfur can be very useful to fabricate cathodes for Li–S batteries with high initial capacity and cycling stability. [ABSTRACT FROM AUTHOR]