Abstract Charge transfer complexes (CT) of novel ethenyl and ethinyl[2.2]paracyclophanes with TCNE and DDQ were prepared and studied. Different behavior was observed depending on the type of donor and acceptor. The values of the association coefficients, stability constants, ionization potentials and the transition energies were determined. Some solid CT-complexes were separated and analyzed. Surprisingly, remarkable differences of the chemical shifts in the 1H-NMR as well as the absorption in the IR spectra were observed.