A dihydroxy-substituted benzothienobenzothiophene, BTBT(OH)2, was synthesized, and its charge-transfer (CT) salt, β-[BTBT(OH)2]2ClO4, was successfully obtained. Thanks to the introduced hydroxy groups, a hydrogen-bonded chain structure connecting the BTBT molecules and counter anions was formed in the CT salt, which effectively increases the dimensionality of the electronic structure and consequently leads to a stable metallic state.