The X-ray structure analyses of tetramethylammonium and tetraethylammonium salts of tetrafluorotetracyanoquinodimethanide (TCNQF(4)(-.)) (NMe(4)(+). TCNQF(4)(-.) and NEt(4)(+). TCNQF(4)(-.)) were performed. In these crystals the TCNQF(4)(-.) molecules form dimers, which are stacked in a plane-to-plane manner to columns. Recrystallization of NMe(4)(+). TCNQF(4)(-.) in the presence of TCNQF(4) (or TCNQ) gave a single crystal of (NMe(4)(+). TCNQF(4)(-.)) 1/2TCNQF(4) (or TCNQ). The crystal is composed of alternating TCNQF(4) (or TCNQ)/TCNQF(4)(-.) and NMe(4)(+) ion layers, and the TCNQF(4) (or TCNQ)/TCNQF(4)(-.) layer adopts a unique packing structure, in which each pair of two TCNQF(4)(-.) molecules is arranged in a completely perpendicular manner to each of one TCNQF(4) (or TCNQ) molecule. The similar TCNQF(4) (or TCNQ)/TCNQF(4)(-.) mixed salt was not obtained in use of NEt(4)(+). TCNQF(4)(-.) at all.