Communication: Synthetic metals based on tetrachalcogenafulvalene donor molecules have received much attention. Unlike the thia-, selena-, and tellura-derivatives, tetraoxafulvalenes (TOFs) are rare, because of difficulties in their preparation and isolation. Here is presented the first unequivocal synthesis, spectral characterization, and X-ray structure determination of TOF derivatives-dibenzo-(see Figure) and dinaphtho-TOF.