Abstract Two optically active molecules were prepared using enantiopure planar chiral [2.2]paracyclophane as chiral building blocks, in which π‐electron systems were stacked at 120° to form a V‐shaped structure. The optical and chiroptical properties of the synthesized molecules were investigated experimentally and theoretically. The chiroptical properties depended strongly on the orientation of the stacked π‐electron systems; in other words, these properties could be regulated by changing the orientation of the stacked π‐electron systems.