Investigations of the tetrathiafulvalene (TTF) derivatives extended by the sigma -bond frameworks, such as saturated heterocycles (3-8) and alkyl groups (9), have been undertaken to explore new molecular-based organic metals. TTF donors with the periphery extended by the cis-fused dioxane ring (3) and by linkage of a dichalocogenolane or dioxane ring (4-6 or 7) produce metallic radical-cation salts. While radical-cation salts of the methylated TTF donor (9a) are semiconductive, the ClO4 and PF6 salts of the ethylated one (9b) exhibit metallic conducting behavior for compressed pellets. The crystal structure of the metallic (4)(2)AsF6 salt is also presented.