Metal‐mediated base pairs have widespread applications, such as in DNA‐metal nanodevices and sensors. Here, we focused on their sugar conformation in duplexes and observed the crystallographic structure of the non‐canonical DNA/DNA duplex containing 2′‐O,4′‐C‐methylene bridged nucleic acid in the presence of AgI ions. The X‐ray crystallographic structure was successfully obtained at a resolution of 1.5 Å. A novel type of AgI‐mediated base pair between the N1 positions of anti‐conformation of adenines in the duplex was observed. In the central non‐canonical region, a hexad nucleobase structure containing AgI‐mediated base pairs between the N7 positions of guanines was formed. A highly bent non‐canonical structure was formed at the origin of AgI‐mediated base pairs in the central region. The bent duplex structure induced by the addition of AgI ions might become a powerful tool for dynamic structural changes in DNA nanotechnology applications.