Preparations, crystal structure analyses, and magnetic property investigations on a new Cu-II(hfac)(2) complex coordinated with two TTF-CH=CH-BTA ligands, where hfac is hexafluoroacetylacetonate, TTF is tetrathiafulvalene, and BTA is 1,3-benzothiazole, are reported together with those of its dicationic AsF6- salt, [Cu(hfac)(2)(TTF-CH=CH-BTA)(2)](AsF6)(2), in which each TTF part is in a radical cation state. In these Cu-II(hfac)(2) complexes, two ligands are bonded to the central Cu atom of the Cu(hfac)(2) part through the nitrogen atom of the 1,3-benzothiazole ring and occupy the two apical positions of the Cu(hfac)(2) complex with an elongated octahedral geometry. These two ligands are located parallelly in a transverse head-to-tail manner, and the Cu(hfac)(2) moiety is closely sandwiched by these two ligands. In the AsF6- salt of the Cu(hfac)(2) complex, each TTF diner is separated by the AsF6- anions and has no overlap with each other within the one-dimensional arrays, resulting in an insulating behavior. Both Cu(hfac)(2) complexes showed the simple Curie-like temperature dependence of paramagnetic susceptibilities (chi(M)), indicating that no interaction exists between the paramagnetic Cu-II d spins. Furthermore, crystal structure analysis and magnetic/conducting properties of a radical cation ReO4- salt of the Cu-I complex with two TTF-CH=CH-BTA ligands, [Cu(TTF-CH=CH-BTA)(2)](ReO4)(2), are also described. Two nitrogen atoms of the ligands are connected to the central Cu-I in a linear dicoordination with a Cu-N bond length of 1.879(9) angstrom. Two TTF parts of the neighboring complexes form a dimerized structure, and such a TTF dimer forms a one-dimensional uniform array along the a direction with a short S-S contact of 3.88 angstrom. Magnetic property measurement suggested the existence of a strongly antiferromagnetic one-dimensional uniform chain of S = 1/2 spins that originate from the radical cation states of the TTF dimers. Due to the construction of the one-dimensional uniform array of the radical cation state of the TTF dimer along the a axis, a semiconducting behavior is observed with sigma(rt) = of 6 x 10(-5) S cm(-1) and an activation energy of E-a = 0.16 eV.