Zero-dimensional (0D)　hybrid　manganese　halides　have　gained　wide　attention　for　the　various　crystal　structures,　excellent　optical　performance　and　scintillation　properties　compared　with　3D　lead　halide　perovskite　nanocrystals.　In　this　work,　a　new　family　of　0D　hybrid　manganese　halides　of　A2MnBr4　(A = BzTPP,　Br-BzTPP,　and　F-BzTPP)　based　on　discrete　[MnBr4]2−　tetrahedral　units　is　reported　as　highly　efficient　lead-free　scintillators.　Excited　by　UV　or　blue　light,　these　hybrids　emit　bright　green　light　originating　from　the　d–d　transition　of　Mn2+　with　near-unity　PLQY　(99.5%).　Significantly,　high　PLQY　and　low　self-absorption　render　extraordinary　radioluminescence　properties　with　the　highest　light　yield　of　80,100　photons　MeV−1,　which　reached　the　climax　of　present　hybrid　manganese　halides　and　surpassed　most　commercial　scintillators.　The　radioluminescence　intensity　features　a　linear　response　to　X-ray　doses　with　a　detection　limit　of　30　nGyair　s−1,　far　lower　than　the　requirement　of　medical　diagnostic　(5.5　µGyair　s−1).　X-ray　imaging　demonstrates　ultrahigh　spatial　resolution　of　14.06　lp　mm−1　and　short　afterglow　of　0.3 ms　showcasing　promising　application　prospects　in　radiography.　Overall,　we　demonstrated　new　hybrid　manganese　halides　as　promising　scintillators　for　advanced　applications　in　X-ray　imaging　with　multiple　superiorities　of　nontoxicity,　facile-assembly　process,　high　irradiation　light　yield,　excellent　resolution,　and　stability.　©　2024　The　Author(s).　Aggregate　published　by　SCUT,　AIEI,　and　John　Wiley　&　Sons　Australia,　Ltd.