<p>Asymmetric Suzuki-Miyaura couplings have proven to be a powerful method towards the efficient and stereoselective construction of diverse stereogenic elements. However, the construction of planar chirality with such methodology has been rarely explored. Here we demonstrate the enantioselective synthesis of planar chiral pillar[5]arenes via asymmetric Suzuki-Miyaura coupling, leading to the successful synthesis of a wide range of planar chiral pillar[5]arenes with wide diversity in both structure and functionality. In addition, facile derivatizations of the resultant planar chiral pillar[5]arenes further enable the synthesis of a giant “ring on ring” macrocycle as an excellent circularly polarized luminescence (CPL) emitter with a dissymmetry factor (<i>g</i>_lum) of −0.021, highlighting the great potential of such synthetic methodology for the creation of novel chiral luminescent materials. This work not only extends the asymmetric cross-coupling methodologies for chiral synthesis but also contributes promising chiral building blocks for widespread applications.</p>