A racemic mixture of three-layered [3.3]paracyclophane ([3.3]PCP), 1, has been resolved into two enantiomers, and their absolute configuration was determined from a comparison of experimental chiroptical properties and density functional theory (DFT) calculations. A simple model comprising two p-xylenes and 1,2,4,5-tetramethylbenzene (durene) was used to explain the origin of the chiroptical properties of the three-layered cyclophane system.