Gelation is an effective way to realize the self‐assembly of nanomaterials into different macrostructures, and in a typical use, the gelation of graphene oxide (GO) produces various graphene‐based carbon materials with different applications. However, the gelation of MXenes, another important type of 2D materials that have different surface chemistry from GO, is difficult to achieve. Here, the first gelation of MXenes in an aqueous dispersion that is initiated by divalent metal ions is reported, where the strong interaction between these ions and OH groups on the MXene surface plays a key role. Typically, Fe2+ ions are introduced in the MXene dispersion which destroys the electrostatic repulsion force between the MXene nanosheets in the dispersion and acts as linkers to bond the nanosheets together, forming a 3D MXene network. The obtained hydrogel effectively avoids the restacking of the MXene nanosheets and greatly improves their surface utilization, resulting in a high rate performance when used as a supercapacitor electrode (≈226 F g−1 at 1 V s−1). It is believed that the gelation of MXenes indicates a new way to build various tunable MXene‐based structures and develop different applications. Fast gelation of Ti3C2Tx MXenes is initiated by divalent metal ions in aquesous solution. Typically, Fe2+ ions eliminate the electrostatic repulsion, networking MXene nanosheets into a 3D structured hydrogel. The wet hydrogel avoids nanosheet restacking and is ideal for applications highlighting the surface utilization, especially as freestanding electrodes for high‐rate supercapacitors.