AbstractMetal coordination compound (MCC) glasses [e.g., metal‐organic framework (MOF) glass, coordination polymer glass, and metal inorganic‐organic complex (MIOC) glass] are emerging members of the hybrid glass family. So far, a limited number of crystalline MCCs can be converted into glasses by melt‐quenching. Here, we report a universal wet‐chemistry method, by which the super‐sized supramolecular MIOC glasses can be synthesized from non‐meltable MOFs. Alcohol and acid were used as agents to inhibit crystallization. The MIOC glasses demonstrate unique features including high transparency, shaping capability, and anisotropic network. Directional photoluminescence with a large polarization ratio (≈47 %) was observed from samples doped with organic dyes. This crystallization‐suppressing approach enables fabrication of super‐sized MCC glasses, which cannot be achieved by conventional vitrification methods, and thus allows for exploring new MCC glasses possessing photonic functionalities.