Abstract Although two‐dimensional (2D) metal–halide double perovskites display versatile physical properties due to their huge structural compatibility, room‐temperature ferroelectric behavior has not yet been reported for this fascinating family. Here, we designed a room‐temperature ferroelectric material composed of 2D halide double perovskites, (chloropropylammonium) 4 AgBiBr 8 , using an organic asymmetric dipolar ligand. It exhibits concrete ferroelectricity, including a Curie temperature of 305 K and a notable spontaneous polarization of ≈3.2 μC cm −2 , triggered by dynamic ordering of the organic cation and the tilting motion of heterometallic AgBr 6 /BiBr 6 octahedra. Besides, the alternating array of inorganic perovskite sheets and organic cations endows large mobility‐lifetime product ( μτ =1.0×10 −3 cm 2 V −1 ) for detecting X‐ray photons, which is almost tenfold higher than that of CH 3 NH 3 PbI 3 wafers. As far as we know, this is the first study on an X‐ray‐sensitive ferroelectric material composed of 2D halide double perovskites. Our findings afford a promising platform for exploring new ferroelectric materials toward further device applications.