Scintillators can be widely applied to the fields of radioactivity detection, space exploration, and medical diagnosis and have attracted great attention. Recently, manganese(II) complexes with high-efficiency phosphorescent emission are expected to be good candidates for new scintillator materials. Herein, we design and synthesize a series of novel nonclassical binuclear neutral manganese(II) complexes with unique coordination modes, in which the crystal structures of CP1 and CP2 contain both four-coordinated and six-coordinated manganese(II) centers and CP3 is formed as a binuclear five-coordinated dichloro-bridged dimer. The single crystals of CP1-CP3 exhibit excellent stability, which can be attributed to their nonionic structures. They all exhibit intense red emission under UV and X-ray irradiation. Among the three manganese(II) complexes, CP1 demonstrates the best luminescence efficiency and X-ray scintillation performance with a high photoluminescence quantum yield (PLQY) of 91.9%, a relative light yield of 21037 photons MeV-1, and a detection limit of 34.45 nGyair s-1. Moreover, X-ray imaging based on CP1 scintillator screen demonstrates a spatial resolution of nearly 6 lp mm-1. As far as we know, this is the first report about stable binuclear neutral manganese(II) complexes for X-ray imaging and opens a new avenue for exploring novel scintillator materials.