Abstract An amphiphilic tetrathiafulvalene (1) was prepared by condensation of tetrathiafulvalene-4-carboxylic acid with reduced Triton X-100 to avoid crystallization. Its charge-transfer (CT) complexation behaviors were examined with a strong electron acceptor, i.e., 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), in solutions. Although tetrathiafulvalene, (4-tetrathiafulvalenyl)methyl acetate (2), and methyl tetrathiafulvalene-4-carboxylate (4) reacted with DDQ to produce a dark red precipitates in CHCl3 and (4-tetrathiafulvalenyl)methyl stearate (3) with DDQ formed black red colloidal dispersions in CHCl3, an equimolar amount of DDQ with 1 in CHCl3 formed a dark red solution without any precipitates. The UV spectrum of the solution of 1 and DDQ in CHCl3 shows a broad peak in near-IR regions. The absorption maximum at 1300 nm (ε = 3.8 × 102 M−1 cm−1) that is tailing to beyond 2000 nm is derived from π-stacked arrangement of the TTF moiety and DDQ. UV–vis absorption spectra of 1 with DDQ in several organic solvents, i.e., acetonitrile, acetone, CH2Cl2, toluene, and CCl4, show that the CT complexation behavior of 1 was highly dependent on the solvent polarity.