AbstractThe electrical properties of complex anion radical salts of 7,7′,8,8′‐tetracyanoquinodimethane with polycations containing sulfur atoms in the main chain were investigated. The influence of the chemical structure of complex and simple salts on their electrical properties is discussed. Complex salts Ks[x, y] containing an odd number of methylene groups between positively charged sulfur atoms show higher electrical conductivity than those with even number of methylene groups between positively charged sulfur atoms. It was found that with simple salts the electrical conductivity increases with the decrease of the distance between S+. For complex salts the electrical conductivity increases if the distance between the donor centers increases. The lowest resistivity values ϱ = 6.46 Ω. cm were found with the complex salts Ks[5,6], whereas the thermal activation energy amounted to 0.015 eV. Electrical properties of these complexes were compared with that of TCNQ complexes with x‐