The 1:1 trans-stilbene (STB)-TCNQ charge-transfer complex has been isolated and its crystal structure determined. It is stable at 150°C under the N2 atmosphere. Charge-transfer band is found at 612 nm with the molar extinction coefficient of 3.21 × 103 mol−1 dm3cm−1 in CH2Cl2 solution and the association constant is 0.31 mol−1dm3 at 295 K. Electrical conductivity is 4.5 × 10−11 Scm−1 at 300 K along the needle axis. The activation energy is 0.83 eV with semiconducting property. Magnetic susceptibility is 5.2 × 10−5 emu mol−1 which is weakly paramagnetic.