Radical cation salts composed of a bis(ethylenedithio)-tetrathiafulvalene (ET) donor with homo-/heterosubstituted Cl/CN anilic acids as purely organic molecular conducting materials formulated as [BEDT-TTF]2[HClCNAn] (1) and [BEDT-TTF][HCl(2)An] (2) have been prepared by electrocrystallization. Compounds 1 and 2 crystallized in the monoclinic space group P2/c for 1 and I2/a for 2, showing segregated donor-anion layers arranged in a alpha'-type donor packing pattern (1) and twisted parallel columns (2), respectively. Single-crystal conductivity measurements show that 1 is a semiconductor with room-temperature conductivity of 10(-2) S cm(-1) and an activation energy E-a of 1900 K.