Leaded brass alloys with high zinc content are classified as dual-phase (α-β′) brass alloys. For these alloys, α-β′ phase transformation induced by thermomechanical processing (TMP) is expected to play a significant role not only in the formation of α and β′ phases and uniformity of lead particles but also in the development of Σ3 boundaries and their variants in the α phase. To assess such impact, the current study has employed two TMP schemes, with each scheme consisting of four cycles of compression and annealing. Samples of the first scheme (TMP-1) were annealed at 670 °C to promote phase transformation from α to β′, as compared to the second scheme (TMP-2) samples annealed at 525 °C. Microstructure examination indicated that TMP-1 scheme fostered a remarkable growth in the area fraction of β′ phase, accompanied by grain coarsening of α and β′ phases. This resulted in the isolation of α grains and less interaction of Σ3 boundaries at trip junctions, and therefore, a reduction in the fraction of Σ3 boundaries occurred in the α phase. On the other hand, the TMP-2 scheme successfully enhanced cluster formation of α grains, enabling further generation of Σ3 boundaries via strain-induced boundary migration mechanism and ultimately leading to breakup of the random boundary network. In addition, the two schemes resulted in limited coarsening of lead particles. Most lead particles were located at the α-βʹ interfaces, which suppressed grain boundary migration via the particle-dragging effect. For both TMP schemes, the initial texture of tension fibers was largely preserved after four cycles for both α and βʹ phases. Nevertheless, the TMP-2 scheme produced texture randomization of the α phase due to increasing the fraction of Σ3 boundaries.