Crop residues returned to the soil are important for the preservation of soil quality, health, and biodiversity, and they increase agriculture sustainability by recycling nutrients. Sugarcane is a bioenergy crop that produces huge amounts of straw (also known as trash) every year. In addition to straw, the ethanol industry also generates large volumes of vinasse, a liquid residue of ethanol production, which is recycled in sugarcane fields as fertilizer. However, both straw and vinasse have an impact on N2O fluxes from the soil. Nitrous oxide is a greenhouse gas that is a primary concern in biofuel sustainability. Because bacteria and archaea are the main drivers of N redox processes in soil, in this study we propose the identification of taxa related with N2O fluxes by combining functional responses (N2O release) and the abundance of these microorganisms in soil. Using a large-scale in situ experiment with ten treatments, an intensive gas monitoring approach, high-throughput sequencing of soil microbial 16S rRNA gene and powerful statistical methods, we identified microbes related to N2O fluxes in soil with sugarcane crops. In addition to the classical denitrifiers, we identified taxa within the phylum Firmicutes and mostly uncharacterized taxa recently described as important drivers of N2O consumption. Treatments with straw and vinasse also allowed the identification of taxa with potential biotechnological properties that might improve the sustainability of bioethanol by increasing C yields and improving N efficiency in sugarcane fields.