A new calixarene-based donor-acceptor system, cone conformer 1, was prepared for the first time. In this compound, the calix[4]arene serves to juxtapose a tri-chloroquinone acceptor near the porphyrin photo-donor plane. As to the conformational control, the cone conformer 1 gave two peaks of phenolic OH groups at 8.40 and 8.43 ppm. This shows that cone conformer 1 is stabilized by intramolecular hydrogen bonds. The fluorescence intensity of 1 was 35% of that for the control compound 2. This means the trichloroquinone group in 1 efficiently quenched the fluorescence of ZnP*. The shortest edge-to-edge separation of the chromophores of 1 is ca. 8 Å (as judged by CPK models). This provides a new calixarene-based supramolecular system in which through-space donor-to-acceptor electron transfer is observed upon photoexcitation.