The 1:1 charge-transfer complex of phenanthrene (PH) and TCNQ has been prepared and characterized. It is stable at 195°C under nitrogen atmosphere. Its charge-transfer band is found at 520 nm (2.38 eV) in the solid state. Longitudinal electrical conductivity is 2.37 × 10−7 Scm−1 at 300 K with activation energy of 0.32 eV. The energy gap (0.64 eV) associated with this semiconductor is much smaller than the energy of the charge-transfer excitation. The diamagnetic susceptibility of this complex is found to be less than the sum of the constituent molecules indicates that PH-TCNQ is weakly paramagnetic.