Depleted uranium will be stainless if a small amount of niobium was added into it, and niobium has good solubility in the γ-phase uranium. Upon cooling, it undergoes phase transformation. U-Nb alloys which is near the monotectoid have a finally martensitic (α") phase at room temperature if the content percent of niobium is from 5 to 8 w.t.%. First principles calculations have been performed to study how the niobium (Nb) atom defects into the γ-uranium and crystal structure of U-12.5 at% Nb alloy. Using DFT calculations, the authors find that the substitutional sites prefer to be occupied by Nb atoms thermodynamically in the γ-phase U. Furthermore, the crystal structure of U-12.5 at% Nb alloy is a monoclinic structure (α"), and the electronic structures characteristic reveals that the electron interactions between Nb atoms and U atoms in the alloy are mainly dominated by 4d orbital of Nb atom and 5f, 6d orbitals of U atom.