The fabrication of two-dimensional crystals (2DCs) has attracted very large interest because it creates materials with various surface structural features and special surface properties. Normally, this is limited to sheets networked together with strong covalent or coordination bonds. Against this understanding, we discovered macroscopic scale free-standing 2DCs in the aqueous dispersions of [Cnmim]X (X = Br, NO3; n = 14, 16, 18) using simultaneous synchrotron small- and wide-angle X-ray scattering techniques. On the other hand, the 2DCs are also a kind of novel hydrogel holding water content up to 98 wt %. This unusual phenomenon is attributed to the weak interactions between imidazole headgroups and counterions. The observation reported in this work is expected to contribute to theorists in their pursuit of the general principles governing the stability of 2D materials. It may also enlighten experimentalists in designing new free-standing 2DCs for various applications.