(R,R,R)-Quaternaphthyls possessing eight and six pyrenes (compounds 4 and 3) displayed intense excimer-CPL. The glum values in solution and in the solid state were +0.034-0.037 and +0.0053-0.0056, respectively. The glum values of 3 and 4 were indistinguishable, indicating that the pyrenes of 3 and 4 assumed the same conformation, even in excited states. The intense CPL was caused by conformationally rigid pyrenes arranged via the cumulative steric effects along the quaternaphthyl axis.