A coordination gadolinium(III) mononuclear complex involving the new redox-active tetrathiafulvaleneamido-2-pyrimidine-1-oxide is synthesized. The X-ray structure of the 1:3 gadolinium complex [Gd(hfac)(3)(TTF-CONH-2-Pym-1-oxide)(3)](CH2Cl2)center dot 0.5C(6)H(14) reveals that the coordination polyhedron of the paramagnetic 4f (S =7/2) Gd-III ion can be described as a 4,4,4-tricapped trigonal prism. The three-coordinated TTF derivatives adopt a fac conformation with a pseudohelicoidal arrangement. A radical-cation salt of this new ligand is reported. Such a coordination complex is an innovative building block for the pi-f system and the introduction of new physical properties.