Metal‐free　molecular　perovskites　have　shown　great　potential　for　X‐ray　detection　due　to　their　tunable　chemical　structures,　low　toxicity,　and　excellent　photophysical　properties.　However,　their　limited　X‐ray　absorption　and　environmental　instability　restrict　their　practical　application.　In　this　study,　cesium‐based　molecular　perovskites　(MDABCO‐CsX3,　X　=　Cl,　Br,　I)　are　developed　by　introducing　Cs+　at　the　B‐site　to　enhance　X‐ray　absorption　while　retaining　low　toxicity.　The　effects　of　halide　modulation　on　the　physical　properties　and　device　performance　are　systematically　investigated.　Among　the　variants,　MDABCO‐CsBr3　exhibited　superior　environmental　stability,　attributed　to　the　optimal　ionic　radius　and　high　chemical　stability　of　Br−.　This　stability　is　further　enhanced　by　a　higher　tolerance　factor,　which　promotes　a　stable　3D　cubic　structure　and　suppresses　ion　migration　within　the　crystal.　Consequently,　MDABCO‐CsBr3‐based　X‐ray　detectors　demonstrated　reduced　ionic　migration,　minimal　dark　current　drift,　and　a　stable　current　response　under　X‐ray　exposure,　achieving　a　high　sensitivity　of　4124　µC　Gy−1　cm−2　and　a　low　detection　limit　of　0.45　µGy　s−1.　Moreover,　the　devices　exhibit　excellent　thermal　stability,　operating　effectively　at　temperatures　up　to　130　°C.　These　results　highlight　MDABCO‐CsBr3　as　a　promising　candidate　for　stable　and　efficient　X‐ray　detection,　expanding　the　applicability　of　molecular　perovskites　in　advanced　radiation　detection　technologies.