A novel electron donor, (MeO)(4)DBTTF (D) forms two kinds of charge-transfer(CT) complexes, black powdered 1:1 (DA) and black needle single crystalline 2:1 (D2A) complexes, with TCNQ (A). The electrical conductivities are 1.5 Omega cm for DA and 67 Omega cm for D2A. For D2A, a single crystal X ray diffraction analysis was performed. It is found that two kinds of D molecules e;ist in a unit cell and the positive charge inhomogeneously distributed over the two D molecules. For DA, the degree of charge-migration from D to A is estimated to be similar to 0.6 from the Raman spectrum.