Niobium (Nb) and its hydrides have been the focus of many studies due to applications as a hydrogen storage material, as a dielectric coating in semiconductor devices and in superconducting radio-frequency cavities. In this paper, we will present the atomic-scale characterization of Nb hydrides using scanning transmission electron microscopy and electron energy loss spectroscopy (EELS) at room and liquid nitrogen temperatures. Although such cavities are formed from ultrahigh purity Nb, using electron beam diffraction, we found that at LN2 temperature, the grains near the surface of cold-worked Nb sheets contain regions exhibiting three different superlattice features, which are identified as β, ε, and ζ-NbHx phases. Z-contrast imaging and EELS at LN2 temperature are utilized to qualify their atomic and electronic structures.