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The issue of managing waste bread is a global concern, with significant environmental and the economic implications. The utilisation of waste bread for bioethanol production, employing energy-saving technology, could prevent these consequences and reduce the consumption of traditionally used fossil fuels. The objective of this study was to evaluate the influence of the type of waste bread (wheat and wheat–rye sourdough) and the mash preparation method on the results of alcoholic fermentation and the concentration of selected congeners in the distillates. The highest fermentation efficiency (96% of theoretical) was achieved for both types of bread through the utilisation of the pressureless starch liberation method combined with simultaneous saccharification and fermentation. The separate saccharification of starch resulted in lower process efficiencies (from 85.75 to 88.60% of theoretical). The application of the native starch hydrolysis method (without starch activation) for the fermentation of wheat bread-based mashes exhibited a higher efficiency (87.85% of the theoretical) than that observed for the wheat–rye bread-based mash sample (83.74% of theoretical). All of the obtained spirit distillates exhibited a low concentration of methanol (≤300 mg/L alcohol 100% v/v) and comply with the requirements of the EU regulation for ethyl alcohol of agricultural origin (rectified spirit). [ABSTRACT FROM AUTHOR]