Abstract: | A chiral electrochemically responsive molecular universal joint (EMUJ) was synthesized by fusing a macrocyclic pillar6]arene (P6]) to a ferrocene‐based side ring. A single crystal of an enantiopure EMUJ was successfully obtained, which allowed, for the first time, the definitive correlation between the absolute configuration and the circular dichroism spectrum of a P6] derivative to be determined. The self‐inclusion and self‐exclusion conformational change of the EMUJ led to a chiroptical inversion of the P6] moiety, which could be manipulated by both solvents and changes in temperature. The EMUJ also displayed a unique redox‐triggered reversible in/out conformational switching, corresponding to an occupation/voidance switching of the P6] cavity, respectively. This phenomenon is an unprecedented electrochemical manipulation of the capture and release of guest molecules by supramolecular hosts. |