Zirconium (Zr) alloys are utilized as structural components for the cores of nuclear reactors due to the excellent combination of their mechanical properties and corrosion resistance under intense neutron irradiation conditions in water. The characteristics of microstructures formed during heat treatments play a crucial role in obtaining the operational performance of parts made from Zr alloys. This study investigates the morphological features of (α + β)-microstructures in the Zr-2.5Nb alloy, as well as the crystallographic relationships between α- and β-phases. These relationships are induced by the β→α(α″) displacive transformation that occurs during water quenching (WQ) and the diffusion-eutectoid transformation that takes place during furnace cooling (FC). To conduct this analysis, samples solution treated at 920 °C were examined using EBSD and TEM. The experimental distribution of α/β-misorientations for both cooling regimes deviates from the Burgers orientation relationship (BOR) at a discrete set of angles close to 0, 29, 35, and 43°. The experimental α/β-misorientation spectra are confirmed by crystallographic calculations for the β→α→β-transformation path based on the BOR. Similar spectra of misorientation angle distribution in α-phase and between α and β phases in Zr-2.5Nb after WQ and FC point to similar transformation mechanisms and the significant role of shear and shuffle in β→α-transformation.