There is a growing interest in applying natural and sustainable methods to improve functional, nutritional, and technological properties of foods. Sprouting and sourdough are promising technological solutions in the bakery industry. This study evaluated the effect of incorporating sourdough (SD) made from unsprouted (USWF) and sprouted whole-wheat flour (SWF) on the technological quality and volatile profile of bread. Sourdoughs were prepared from USWF or SWF, obtained under controlled conditions (20 °C for 24 h), and propagated at 30 °C for 7 days. Breads were formulated by substituting 20% of USWF with ripe sourdoughs—SB(USWF) and SB(SWF), respectively—and compared with a control bread (CB) made exclusively with USWF. Bread quality and volatile organic compounds (VOCs) were assessed. Sourdough-substituted breads exhibited improved specific volume (30–40%) and softer crumb texture (20–60% less firmness), both post-baking and following storage. Additionally, SB(SWF) led to higher crust browning and distinct VOCs, such as ethyl-heptanoate, heptanol, and geranyl-acetone, which were absent in SB(USWF) and CB. The compounds are associated with pleasant aromas, which may represent a potential advantage of using SD made from SWF. Overall, combining sprouting with sourdough improves whole-wheat bread's texture and aroma, providing a promising strategy to improve sensory attributes and consumer acceptability.