The one-pot synthesis of a Cu(II) complex with partially oxidized tetrathiafulvalene (TTF) moieties in its capping MT-Hsae-TTF ligands, [CuII(MT-sae-TTF)2] [CuICl2] was realized by the simultaneous occurrence of Cu(II) complexation and CuIICl2 mediated oxidation of TTF moieties. The crystal structure was composed of one-dimensional columns formed by partially oxidized TTF moieties and thus the cation radical salt showed relatively high electrical conductivity. Tight binding band structure calculations indicated the existence of a Peierls gap due to the tetramerization of the TTF moieties in the one-dimensional stacking column at room temperature, which is consistent with the semiconducting behavior of this salt.