In summary, our study draws inspiration from the biomineralization process and the structure of organic polymers, and demonstrates that weakening the strong ionic bonds in solid structure can turn the rigid inorganic materials into flexible ones. These findings have important implications for the development of flexible inorganic materials with exceptional properties, and they emphasize the control of solid phase in future materials research. Furthermore, we believe that the inorganic ionic polymerization will be a potent methodology to realize the control of solid structures. Following this understanding, there will be a promising way to combine the unique properties of inorganic materials and polymers, such as hardness and elasticity, thermal stability and plasticity, toughness and flexibility, etc. within one material, directing to unprecedented properties and functions.