AbstractX‐ray detectors have obtained great attention in medical diagnostics, security checks, and space exploration. However, ion migration of X‐ray detectors results in dark current drift, low signal‐to‐noise ratio, and degradation of detection performance. Here, ion migration properties of Li2ZrTeO6 and ZrTe3O8 are comprehensively investigated by theoretical analysis and experimental results. ZrTe3O8 single crystal exhibits a high migration barrier of O2− ion (1.89 eV), a high ion activation energy (992.6 meV), and an ultralow dark current drift (3.16 × 10−9 nA cm−1 s−1 V−1) due to the absence of Li+ cations and the disconnecting of adjacent ZrO6 octahedra, which is better than Li2ZrTeO6 single crystal. These results show that the absence of low atomic number elements and the disconnecting of adjacent octahedra in crystal structure can inhibit ion migration essentially. Owing to a high resistivity, a high mobility lifetime product, suppressed ion migration, and the lone‐pair electrons enhancement effect of detection performance for Te4+ cations, ZrTe3O8 X‐ray detector shows a high sensitivity of 348 µC Gy−1 cm−2 and an ultralow detection limit of 15.4 nGyair s−1. This work proposes an effective strategy to inhibit ion migration and proves the enhancement effect of detection performance for the cations containing lone‐pair electrons.