Preparation of 5,15-dithiaporphyrin copper(II) complex was carried out by treatment of 5,15-dithiaporphyrin free-base with copper(II) acetate. X-ray diffraction analysis elucidated its dimeric structure in the solid state, in which the meso-sulfur atom served as an axial ligand to each pentacoordinated Cu ( II ) center. Temperature dependent magnetic susceptibility of the complex was measured to reveal the weak antiferromagnetic interaction between two Cu ( II ) centers in the solid state. 5,15-dithiaporphyrin Cu ( II ) complex was converted into 10-thiacorrole Cu ( II ) complex in good yield upon heating with triphenylphosphine in refluxing toluene.