AbstractOptically active X‐shaped dimers based on the planar chiral [2.2]paracyclophane have been synthesized. The dimers consist of stacked p‐arylene‐ethynylenes with phenyl, naphthyl, and anthryl groups as terminal units. The optical and chiroptical properties of the dimers and the corresponding model compounds were investigated. The naphthalene‐containing dimer exhibits an intense circularly polarized luminescence (CPL) signal with a high dissymmetry factor (glum) in the order of 10–3 in addition to a high ϵ and good photoluminescence quantum efficiency, which indicates that this compound is a highly emissive CPL material.