A viologen‐based Borromean entangled porous framework was found to be sensitive to both CuKα and MoKα X‐ray sources, showing rapid photochromic response and recovery within one minute. The X‐ray‐induced photochromic process is accompanied by a reversible single‐crystal‐to‐single‐crystal (SC‐SC) structural transformation, an unprecedented phenomenon for X‐ray sensitive materials. The complex can be further processed into portable thin films for detecting the dose of the X‐ray exposure. Moreover, the photochromism can occur over a broad temperature range of 100–333 K, both in the form of single crystals and thin films, making it a potential candidate for practical indoor and outdoor applications. X‐ray specs: A viologen‐based Borromean‐entangled porous framework was found sensitive to X‐rays and undergo a rapid photochromic response and recovery. This process is accompanied by a reversible single‐crystal‐to‐single‐crystal transformation. The material can be further processed into a thin film for detecting the dose of X‐ray exposure.