Two salts of the dissymmetric TTF-derivative 4-cyanobenzene-ethylenedithio-tetrathiafulvalene (4-CNB-EDT-TTF) with bromide and tribromide anions and with different stoichiometries, namely, (1:1) (4-CNB-EDT-TTF)-Br 3 (1) and (4:1) (4-CNB-EDT-TTF) 4 Br (2), were obtained by electrocrystallization and diffusion methods, respectively. The crystal structures of these compounds, as determined by single-crystal X-ray diffraction, are based on head-to-tail donor dimers with ring over ring overlap and donor stack arrangement, interleaved by anions depending on the (1:1) or (4:1) salt, respectively. The 4:1 salt behaves as a Mott insulator. In both salts, the donors are connected to adjacent donors through C−N•••H−C interactions, which can be described as an modified R 2 4 (10)* synthon for 1 and a combination of R 2 2 (10) and R 2 4 (10) synthons for 2.