A number of notable studies on pure ionic clathrate hydrates have utilized their unique ionic characteristics for electric applications, including their use as an electrolyte for nickel-metal hydride batteries. Although quaternary ammonium salt hydrates have recently been applied to gas separation and storage areas with the expectation of the small co-guest occupancy in empty cages, most of the researches have been oriented to macroscopic approaches based on hydrate phase equilibria and many other process variables. On the other hand, spectroscopic analyses for identifying the structure transition of ionic clathrate hydrates together with a comprehensive consideration of their complex phase patterns have not yet been reported in spite of their importance to the energy and environmental fields. Accordingly, in this study, we present the report of an extraordinary structural transition accompanying the occurrence of more than two coexisting clathrate hydrate phases and channel-induced tuning pattern in ionic double hydrate systems. In particular, the tuning observation uniquely occurring in the ionic clathrate hydrates is quite surprising, even though the tuning behavior is more commonly observed in the non-ionic hydrate systems. The remarkable feature of this work is that the icy ionic hydrate materials can be effectively used in energy devices. Moreover, the microscopic analyses of ionic clathrate hydrates for identifying the physicochemical characteristics are expected to provide new insights into a variety of inclusion chemistry fields.