In general, FeCrAl alloys are faced with the separation of the high-chromium solid solution into α and α′ phases. For the Fe-25Cr-5Al-RE alloy, it is imperative to investigate the structure and morphology and their effect on the alloy’s mechanical properties. In this paper, XRD is used to reveal the presence of α and α′ phases. Based on XRD data, Rietveld refinement combined with quantitative texture analysis is carried out to determine the lattice constants and the harmonic coefficients. Then, SEM and TEM techniques are employed to provide an insight into the α′ phase and its morphology. The percentage total elongation at fracture is anti-correlated with the lattice of the α′ phase and the generalized harmonic coefficients C41.