defects, interfaces, and grain boundaries, and are thought to be a major source of qubit decoherence at millikelvin temperatures. In addition to Al, Nb is a commonly used metalization layer for superconducting qubits. Consequently, a significant effort is required to develop and qualify processes that mitigate defects in Nb films. As the fabrication of complete superconducting qubits and their characterization at millikelvin temperatures is a time and resource intensive process, it is desirable to have measurement tools that can rapidly characterize the properties of films and evaluate different treatments. Here we show that measurements of the variation of the superconducting critical temperature Tc with an applied external magnetic field H (of the phase boundary Tc−H) performed with very high resolution show features that are directly correlated with the structure of the Nb films. In combination with x-ray diffraction measurements, we show that one can even distinguish variations quality and crystal orientation of the grains in a Nb film by small but reproducible changes in the measured superconducting phase boundary.