The objective of this study was to obtain two types of fuels, i.e., bioethanol and biogas, in a sequential combination of biochemical processes from lignocellulosic biomass (corn straw). Waste from the agricultural sector containing lignocellulose structures was used to obtain bioethanol, while the post-fermentation (cellulose stillage) residue obtained from ethanol fermentation was a raw material for the production of high-power biogas in the methane fermentation process. The studies on obtaining ethanol from lignocellulosic substrate were based on the simultaneous saccharification and fermentation (SSF) method, which is a simultaneous hydrolysis of enzymatic cellulose and fermentation of the obtained sugars. Saccharomyces cerevisiae (D-2) in the form of yeast cream was used for bioethanol production. The yeast strain D-2 originated from the collection of the Institute of Agricultural and Food Biotechnology. Volatile compounds identified in the distillates were measured using gas chromatography with flame ionization detector (GC-FID). CH4 and CO2 contained in the biogas were analyzed using a gas chromatograph in isothermal conditions, equipped with thermal conductivity detector (katharometer) with incandescent fiber. Our results show that simultaneous saccharification and fermentation enables production of bioethanol from agricultural residues with management of cellulose stillage in the methane fermentation process.