AbstractA series of axially chiral 1,1′‐binaphthyls with trialkylsiloxy (OSiR3) groups were synthesized. Among them,1 a–cpossessing OSiR3groups at the 7,7′‐positions and methyl groups at the 2,2′‐positions were liquids at room temperature, and the neat liquids showed circularly polarized luminescence (CPL) (R=Bu;Φfl,liquid=0.21, |glum,liquid|=1.6×10−3). The |glum,liquid| value is the highest of pure liquids. These compounds remained liquid over a broad range of temperatures, down to −50 °C. Time‐dependent DFT calculations indicated that in the excited state, the binaphthyls adopt atransoidconformation with a small angle between the electric and magnetic transition dipole moments (θμ,m=77°), which is a key factor in their CPL activity. The best binaphthyl dihedral angle in the excited state is approximately 110°.