We found that novel amphiphilic tetrathiafulvalene (TTF; 1) organized into supramolecular assemblies by the addition of electron acceptor 2,3,5,6-tetrafluoro-7,7'f,8,8'f-tetracyano-p-quinodimethane (F4TCNQ) at the air-water interface. The assemblies on the air-water interface can be transferred onto the surface of mica and the morphologies of transferred films were investigated by AFM. The morphology of Langmuir-Blodgett films strongly depended on the ratio between 1 and F4TCNQ. Film of 1:1 mixture of 1 and F4TCNQ formed nanoscopic wires having an average dimension of 5.0 (height) × 70 (width) × 3000 (length) nm. On the other hand, the film of 2:1 mixture of 1 and F4TCNQ showed the mixed domains of wires and flat monolayers. Thus, the completely charge-transferred complex (1+)(F4TCNQ-) formed one-dimensional nanowires having a micrometer length. Room temperature electrical conductivities of cast film for 1:1 and 2:1 mixed layers of 1 and F4TCNQ were 2.4 × 10−4 and 8.0 × 10−5 S cm−1, respectively.