Compared to conventional gels, eutectogels encompassing deep eutectic solvents (DESs) circumvent the shortboards including poor temperature resistance, high cost, and undesired toxicity. However, existing eutectogels suffer weak intra‐ and interchain interactions, which culminates in vanishing autofluorescence, weak mechanic and feeble adhesion. Although myriad strategies have been proposed to boost the polymer/polymer interactions within gels, the processes are time‐consuming, which are not suitable for mass production or emergent deployment. Herein, to deal with it, a facile solvation chemistry is leveraged to build dynamic rigid network via incorporating active polymer backbones and DESs. Within these eutectogels, DESs play a magnet‐like role, and physically cluster polymer chains together via multiple noncovalent forces, thus intensifying polymer/polymer and DESs/polymer interactions. This solvation network bestows rare autofluorescence and unprecedentedly high strength, toughness, and adhesion among reported analogues, even in harsh conditions. Moreover, the mechanism of solvation chemistry is fully scrutinized for the first time. It is believed that this facile strategy can be easily expanded to the orchestrations of other soft materials.