A series of 4-aryl-1,1-dicyanobutenes (1a–1f) with different substituents were synthesized to control the intramolecular donor–acceptor or charge-transfer (C–T) interactions in the ground state. Photoexcitation of these C–T substrates led to competitive cyclization and rearrangement, the ratio being critically controlled by various environmental factors, such as solvent polarity, temperature and static pressure, and also by excitation wavelength and supramolecular confinement (polyethylene voids). In non-polar solvents, the rearrangement was dominant (>10 : 1) for all examined substrates, while the cyclization was favoured in polar solvents, in particular at low temperatures. Selective excitation at the C–T band further enhanced the cyclization up to >50 : 1 ratios. More importantly, the cyclization/rearrangement ratio was revealed to be a linear function of the C–T transition energy. However, the substrates with a sterically demanding or highly electron-donating substituent failed to give the cyclization product.