The use of photoreactions such as photoredox catalysts in asymmetric synthesis has been expansively recognized as expedient procedure over the past decade. In this paper, a potential application of photoreaction of Charge-Transfer (CT) complex for asymmetric synthesis is described. In chiral donor-acceptor systems, excitation wavelength, along with other environmental factors such as solvent polarity and temperature, plays more substantial role in determining the stereoselectivity of the photochemical outcomes. Accordingly, the excited CT complex produced upon the selective CT-band excitation behaves completely different from the conventional exciplex, which is formed by the direct excitation of donor or acceptor. Such unique wavelength effect, together with other entropic controls, may possibly come to be valuable means in asymmetric photochemical synthesis for the future.