Bismuth vanadate (BiVO4) exhibits large absorption efficiency for hard X‐rays, which endows it with a robust capacity to attenuate X‐ray radiation across a broad energy range. The anisotropic properties of BiVO4 allow for the manipulation of their physical and chemical characteristics through crystallographic orientation and exposed facets. In this study, the issue of heavy recombination caused by sluggish electron transport in BiVO4 is successfully addressed by enhancing the abundance of the (040) crystal face ratio using a Co2+ crystal face exposure agent. The facet‐dependent modifications exhibit excellent and balanced intrinsic charge transport properties, and finely optimize both the sensitivity and detection limit of BiVO4 X‐ray detectors. As a result, ultra‐stable BiVO4 metal oxide X‐ray detectors demonstrate a high sensitivity of 3164 µC Gyair−1 cm−2 and a low detection limit of 20.76 nGyair s−1 under 110 kVp hard X‐rays, establishing a new benchmark for X‐ray detectors based on polycrystalline Bi‐halides and metal oxides. These findings highlight the significance of crystal orientation in optimizing materials for X‐ray detection, setting a new sensitivity record for X‐ray detectors based on polycrystalline Bi‐halides and metal oxides, which paves the way for the development of advanced, low‐dose, and highly stable imaging systems specifically for hard X‐rays.