Absorption, fluorescence and excitation spectra of different terminally substituted polyenes have been recorded in the UV-Vis region. The observed intramolecular unidirectional energy transfer from a donor substituent to an acceptor at the other end of the chain is influenced but not inhibited by incorporation of a spacer into the polyene chain. In molecules without a spacer, internal conversion within the supermolecule can explain the observed transfer of energy. In molecules with a spacer interrupting the polyene chain the observed intramolecular energy transfer can be explained in terms of Förster transfer.