A comprehensive study into the potential of bioprocessing techniques (sourdough fermentation and technological aids) for improving the technological, sensory, and nutritional properties of breads made using brewer's spent grain (BSG) was undertaken. Xylanase and dough conditioner altered the mixing and pasting properties of the flours, improved the specific volume and texture of breads and delayed staling in BSG breads when added to both sourdough and non-sourdough BSG breads. The aromatic properties were determined by volatile analysis and were influenced by sourdough fermentation. Ferulic and 4-coumaric acids were the main phenolic acids found in insoluble bound form in BSG flour, while the phenolic profile was different for the free extracts. Sourdough fermentation and the use of enzymes increased the antioxidant capacity of breads.