Li-doped pentacene has been developed by using an electrochemical approach; that is, constant-potential electrolysis. Li-doped pentacene was characterized by Raman spectrometry and x-ray diffraction measurements. Lithium doping introduces a modification of the C-H vibrational modes located at the end of pentacene molecules. A low doping level has been observed for electrochemical synthesis of Li-doped pentacene, and lithium species are supposed to be intercalated between the two-dimensional pentacene layers. The lithium-doped pentacene exhibits a conductivity of ∼6× 10-3 S cm-1.