Complementary characterization techniques were used to investigate two commercial Zr-Nb alloys exposed in reactor to understand how the corrosion process is affected by changes in the oxidation state of niobium. Electron energy-loss spectroscopy analysis was carried out to better understand the oxidation state of niobium in the β phase found in dual-phase Zr-2.5Nb and partially recrystallized Zr-2.5Nb alloys irradiated to different damage levels. The different rates of oxidation of niobium in different materials (or samples) are attributed to the manner in which the microstructure of the β phase develops when incorporated into the oxide. Transmission electron microscopy and atom probe tomography were used to show that most of the original β-Zr phase found in the as-received dual-phase Zr-2.5Nb has decomposed to form β-Nb precipitates at 1.9 dpa and 25.2 dpa, whereas energy-dispersive X-ray spectroscopy results show the β-Zr phase found in partially recrystallized Zr-2.5Nb has not decomposed after three cycles in reactor. The possible cause of these different behaviors of the β-Zr phase is discussed. The rate at which niobium in the β phase is oxidized and released into the surrounding oxide controls the aliovalent niobium composition in solid solution and contributes to the charge-balancing effect. These results can help to explain the measured reduced oxidation rate. Furthermore, the oxidation state of niobium in the β phase is compared with results from a different study by spatially resolved X-ray absorption near-edge spectroscopy on the oxidation state of niobium in solid solution in low-tin ZIRLO irradiated for three cycles in reactor that shows a similar “delayed oxidation” phenomenon. All of these results are combined to discuss the overall effect of niobium on the in-reactor corrosion rate of the Zr-Nb alloys.