0D hybrid metal halide (HMH) luminescent glasses have garnered significant attentions for its chemical diversity in optoelectronic applications and it also retains the skeleton connectivity and coordination mode of the crystalline counterparts while exhibiting various physics/chemistry characteristics distinct from the crystalline states. However, understanding of the glass-forming ability and the specific structural origins underpinning the luminescent properties of 0D HMH glasses remains elusive. In this review, it is started from the solid-liquid phase transition and thermodynamic analysis of 0D HMHs formed through melt-quenching, and summarize the current compounds capable of stably forming glassy phases via chemical structural design. The structural characterization methods are further discussed and highlight the exceptional transparency, specific luminescent properties, and glass crystallization behaviors. Moreover, the application prospects demonstrated by these 0D HMH glasses have been presented accordingly in X-ray detection and imaging, anti-counterfeiting, and information encryption. Finally, perspective is offered into the future development of this emerging family of 0D HMH glasses and their applications.