Lignocellulosic waste is one of the most abundant renewable energy sources. However, pretreatment or complex microbial consortia are usually required for the biological transformation into energy products. This study demonstrates the direct transformation of raw rice straw biomass into electricity and hydrogen without any pretreatment by employing a single yeast strain, Cystobasidium slooffiae JSUX1, in microbial fuel cells (MFCs). The yeast-MFCs exhibit a maximum power density of 28.56 ± 2.54 mW/m2 with simultaneous production of hydrogen gas (4.9 ± 0.52 L/m3) from raw straw. Further analysis reveals that enzymes secreted by the yeast strain degraded rice straw into sugars or organic acids, serving as fuel for electricity and hydrogen production. In addition, humic acid (HA) and Fe-HA derived from biomass consumption serve as electron mediators for extracellular electron transfer (EET) in MFCs. This study demonstrates the power of the yeast strain for renewable energy recovery from straw, diversifying the toolbox for the lignocellulose industry.