The formation of the molecular complexes of some phenylfurans with TCNE has been investigated by spectroscopic methods. The formation constants were determined by graphical and iterative procedures and some thermodynamic parameters were calculated. The formed molecular complexes were π ones. Diphenylfuran proved to be a much stronger electron donor than phenylfuran and the latter stronger than furan. Results at hand suggest that the donors investigated assume an all-planar conformation.