One‐Step Assembly of α‐Aryl‐Substituted DOTAs as Superior and Universal Platforms for Multifunctional Theranostics

α‐Substituted DOTAs are promising chelators for MRI contrast agents owing to the improved coordination stability and relaxivity of the corresponding Gd(III) complexes. However, their broader application is limited by significant synthetic challenges arising from their multi‐component nature. In this work, we report—for the first time—the use of multi‐component reactions (MCRs) to assemble all necessary building blocks of α‐aryl‐substituted DOTAs in a single step. This strategy yields derivatives with faster coordination kinetics. Furthermore, we extend their application to luminescent lanthanide probes, achieving improved photophysical properties. This MCR approach offers a versatile solution for establishing a library of functionalized diagnostic and therapeutic agents. We are convinced that this work will reshape the field, inspiring broader exploration of α‐aryl‐substituted DOTA derivatives and unlocking their full potential in next‐generation biomedical applications.