We present the first liquid crystalline (LC) binaphthyl derivatives, in which the rigid rod-like substituents containing phenylcyclohexyl mesogenic cores are introduced into the 2, 2', 6, and 6' positions of the chiral binaphthyl rings. The binaphthyl derivatives show enantiotropic smectic A phase, but neither chiral nematic nor chiral smectic phase. The present quadri-substituted binaphthyl derivatives gave larger values in twisting power (PM), compared with the non-substituted and di-substituted binaphthyl derivatives.