A new chiroptical compound, (E)-(R-p,R-p)-1,2-bis(4-methyl-[2]paracyclo[2](5,8)quinolinophan-2-yl)et hene (trans-RPQE) has been synthesized, and its photoresponse has been investigated through steady state and time-resolved absorption and emission spectroscopies and theoretical calculations. To elucidate the relaxation mechanism of trans-RPQE after photoexcitation, the photophysics of the 2,4-dimethyl-[2]paracyclo[2](5,8)quinolinophane chromophore has also been studied. The quantum yields of the different relaxation paths for trans-RPQE have been determined. It emerges that in addition to thermal and radiative routes, trans-RPQE also photoisomerizes with a quantum yield of 8%. Trans- and cis-RPQE isomers are pseudoenantiomers exhibiting appreciably different CD spectra, whereby RPQE can be a model for the design of new promising chiroptical photoswitches.