A planar-chiral pillar[5]arene with cyclohexylmethoxy side chains and a pendant diphenylphosphine was prepared and used as a chiral ligand in asymmetric reactions. Chirality transfer from the planar-chiral pillar[5]arene scaffold to the chiral biaryl moiety was demonstrated by circular dichroism (CD) spectroscopy, single-crystal X-ray diffraction analysis, and asymmetric catalysis.