In the conventional scenario, it is believed that a hydrogel consists of polymer structural network filled with water droplets, a typical two-phase coexisting structure, while the polymer-water interfacial layer might not be a substantial component in determining the structure and functionality. Unfortunately, it is challenging to unveil the properties of the interfacial layer if any, owing to the multiple phase nature and structural complexity of hydrogel. In this work, the morphology and microstructures of the well-known non-covalent bonding dominant polyacrylonitrile (PAN)-based hydrogels are characterized, confirming that the as-prepared hydrogels do consist of polymer-network and filled water droplets. The dielectric relaxation behaviors in the ice-hydrogel state with different water/ice content are investigated in details by means of dielectric relaxation spectroscopy (DRS), in order to avoid the electrode polarization (EP) effect non-negligible in liquid-hydrogels particularly in the low-frequency range. The DRS data demonstrate the remarkable dielectric response contributed from the polymer-ice interfacial layer which likely accommodates a high density of polar molecules / dipoles. The temperature-dependent dielectric relaxation behaviors of the ice-hydrogels with different water contents are discussed, and the thermal-activation energy for the interfacial polar structure may be likely extracted from the dielectric loss peak data. It is found that this energy is roughly consistent with the typical bonding energy of non-covalent bonding dominant hydrogels. This study represents a substantial step towards understanding the interfacial coupling in hydrogels, an issue less touched so far.