Metal‐Free Basic Guanidinium Ionic Liquid as Dual Catalyst/Solvent for Room‐Temperature Epoxide Aminolysis to Access β‐Amino Alcohols

β‐Amino alcohols represent privileged structural scaffolds widely distributed in natural bioactive molecules and versatile synthetic building blocks, with extensive applications in pharmaceutical manufacturing, functional material construction, and asymmetric organocatalysis. Herein, we disclose a mild, highly efficient ring‐opening aminolysis reaction between aromatic amines and epoxides enabled by a metal‐free basic guanidinium ionic liquid [HTMG ⁺ ][TFE ⁻ ] at ambient temperature. This bifunctional ionic liquid simultaneously acts as a catalytic mediator and nontoxic green reaction medium, which fundamentally differentiates it from conventional catalytic systems that demand elevated heating, metal additives, and extra volatile organic solvents. The developed halogen‐ and metal‐free catalytic platform eliminates external cocatalysts, hazardous organic diluents, and harsh reaction conditions and exhibits broad functional group compatibility to rapidly furnish a diverse array of medicinally significant β‐amino alcohol derivatives with high isolated yields. Notably, [HTMG ⁺ ][TFE ⁻ ] achieves complete substrate conversion within a short reaction time under mild ambient conditions, retains outstanding catalytic performance after five successive recovery cycles, and delivers satisfactory product yields in gram‐scale synthetic operations. This work demonstrates the great application potential of task‐designed basic ionic liquids in organic synthetic transformations and establishes a practical, sustainable, and metal‐free synthetic pathway for constructing high‐value pharmaceutical β‐amino alcohol skeletons, which further advances the development of environmentally benign green synthetic chemistry.