Smart structures with manipulatable properties are highly demanded in many fields. However, there is a critical challenge in the pursuit of transparent windows that allow optical waves (wavelength of µm–nm) for transmitting while blocking microwave (wavelength of cm) in terms of absorbing electromagnetic energy, specifically for meeting the frequency requirement for the 5th generation (5G) mobile networks. For fundamentally establishing novel manipulatable microwave absorbing structures, here, new polymeric aqueous gels as both optically transparent materials and microwave absorbing materials are demonstrated, in which polar networks play significant roles in attenuating electromagnetic energy. By manipulating the hydrogen bonding networks, the resulting optically transparent solid‐state gels are able to offer the capabilities for absorbing microwaves. Interestingly, such gels can be switched into an optically opaque state via converting the amorphous state into a polycrystal state when the temperature is decreased. Such ionic conductive gels can endow the assembled sandwich windows with effective microwave absorbing capability in the range of 15–40 GHz, covering a branch of 5G frequency bands. The results highlight a new strategy for using ionic conductive gels to design and fabricate manipulatable microwave stealth structures for various applications.