Optically active dendrimers, containing a planar chiral [2.2]paracyclophane as the X ‐ shaped core unit, were synthesized. Gram ‐ scale optical resolution and transformations of 4,7,12,15 ‐ tetrasubstituted [2.2]paracyclophanes were also carried out. The high ‐ generation dendrons effectively absorbed UV light and transferred the energy to the core, resulting in high photoluminescence from the core. In addition, the dendrons sufficiently isolated the emissive X ‐ shaped core, and intense circularly polarized luminescence was observed from thin dendrimer films. More information can be found in the Full Paper by Y. Morisaki, Y. Chujo et al. on page 2291 ff. [ABSTRACT FROM AUTHOR]