This study explores the enhancement of proton conductivity in hydrogen-bonded organic frameworks (HOFs) through vitrification, a strategy to eliminate grain boundary effects. By rapidly melt quenching kinetically stable HOF-SXU-8 to form a glassy state (HOF-g), significant improvements in proton conductivity were achieved without the need for humidity control. The proton conductivity of HOF-g increased from 1.31×10⁻⁷ S cm⁻¹ to 5.62×10⁻² S cm⁻¹ at 100 °C, with long-term stability tests showing minimal performance degradation. Molecular dynamics (MD) simulations and X-ray total scattering experiments revealed that HOF-g consists of three types of clusters: 1,5-Naphthalenedisulfonic acid (1,5-NSA) anion clusters, N,N-dimethylformamide (DMF) molecule clusters, and H⁺·H₂O clusters. The H⁺ plays a crucial role in bridging these clusters, and the high conductivity is primarily attributed to H⁺ on H₂O. These findings provide valuable insights for optimizing HOFs and advancing energy conversion and storage devices.This study explores the enhancement of proton conductivity in hydrogen-bonded organic frameworks (HOFs) through vitrification, a strategy to eliminate grain boundary effects. By rapidly melt quenching kinetically stable HOF-SXU-8 to form a glassy state (HOF-g), significant improvements in proton conductivity were achieved without the need for humidity control. The proton conductivity of HOF-g increased from 1.31×10⁻⁷ S cm⁻¹ to 5.62×10⁻² S cm⁻¹ at 100 °C, with long-term stability tests showing minimal performance degradation. Molecular dynamics (MD) simulations and X-ray total scattering experiments revealed that HOF-g consists of three types of clusters: 1,5-Naphthalenedisulfonic acid (1,5-NSA) anion clusters, N,N-dimethylformamide (DMF) molecule clusters, and H⁺·H₂O clusters. The H⁺ plays a crucial role in bridging these clusters, and the high conductivity is primarily attributed to H⁺ on H₂O. These findings provide valuable insights for optimizing HOFs and advancing energy conversion and storage devices.