Solid-state ion conductors are significant class of materials for battery,fuel cell,electrocatalysis,and artificial ion channel,etc.Not only to achieve high ion conductivity,the control of temperature region of ion conduction,or switching of ion conduction by external stimuli is important challenge for application.Control of mechanical property and electrochemical stability are also required for solid-state ion conductive materials.Coordination Polymer(CP)or Metal Organic Framework(MOF)constructed from metal ions and bridging molecular ligands are promising materials for solid-state ion conductors.[1]Some CP/MOF crystals offer anhydrous H+conductivity over 10-3 S cm-1 at 120℃.[2]Recently we have focused on the glassy state of CP/MOF crystals(Fig.1).Glassy state is in general isotropic and dynamic compared with the crystalline state which will be advantageous for ion conductivity.We found several CP/MOF crystals melt as heating,and accordingly form glassy state.[3]Some CP/MOF crystals directly transform to glassy state by mechanical milling.[4]In both cases,we found significant improvement of H+conductivity compared with the crystalline state.X-ray total scattering and solidstate NMR experiments suggest the glassy states retain the identical coordination geometry around the metal ions,and even network structures.Design of ion conduction pathway in CP/MOFs under crystal/glass states will be discussed.