Deformed two-phase Zr–2.5Nb was subjected to 700 °C annealing and associated coarsening. After primary recrystallization, the second-phase body- centered cubic b was well dispersed on the grain boundaries of hexagonal a matrix. Prolonged annealing led to the presence of the b, mainly at the a tri-junctions. The two-phase coarsening was associated with clear trends of widening in the second- phase size distribution and changes in phase boundary nature. The former is contrary to what is expected. Changes in phase boundary nature were through increased concentration of 45°[0 0 1] phase boundaries—good-fit interfaces, present in larger b particles, which were estimated to have higher three-dimensional lattice coincidence and hence lower energy. Simple analytical modeling, assuming dissolution controlled particle coarsening and a lower interfacial energy of the phase interface with the 45°[0 0 1], was shown to explain these experimental observations.