The intensity and handedness of circularly polarized luminescence (CPL) have been successfully controlled by dynamic molecular motion in the solution state. Bis(boron difluoride) complexes with chiral salen ligands were synthesized and their photophysical properties were investigated. While these complexes showed rapid molecular rotation about the C‐N bond axis in solution at room temperature, two conformers assigned as atropisomers were observed in the NMR spectra at low temperature. Furthermore, the equilibrium of these atropisomers was found to change depending on the external environment, such as solvent and temperature, allowing the precise control of intensity and handedness of CPL without luminescence color shifts. Theoretical calculations based on density functional theory (DFT) revealed that intramolecular chiral exciton coupling is the key to the changes in the CPL properties.