Unprecedented strong phosphorescent emission in the crystalline state is observed for a variety of vaulted trans-bis(salicylaldiminato)platinum(II) complexes which are newly synthesized as a third coordination mode of well-studied bis(salicylaldiminato) complexes. This Communication describes the dynamic photophysical properties of these complexes in the liquid and crystalline states and a mechanistic rationale for the strong emission in the crystalline state.