A novel room‐temperature liquid crystal of tetraphenylethylene derivative (TPE‐DHAB) was synthesized using an ionic self‐assembly strategy. The TPE‐DHAB complex exhibits typical aggregation‐induced emission properties and a unique helical supramolecular structure. Moreover, the generation and handedness inversion of circularly polarized luminescence (CPL) can be achieved through further chiral solvation, providing a facile approach to fabricate room‐temperature liquid crystalline materials with controllable supramolecular structures and tunable CPL properties through a synergistic strategy of ionic self‐assembly and chiral solvation process.