Abstract2‐Amino[2.2]paracyclophane reacts with salicylaldehyde or 2‐hydroxyacetophenone to yield imines that then give access to a new series of boranils (8b–d) upon complexation with BF₂. These novel boron‐containing compounds display both planar and axial chiralities and were examined experimentally and computationally. In particular, their photophysical and chiroptical properties were studied and compared to newly prepared, simpler boranils (9a–d) exhibiting axial chirality only. Less sophisticated chiral architectures were shown to demonstrate overall stronger circularly polarized luminescence (CPL) activity.