Synthetic approach to the construction of new tetrathiafulvalene (TTF) donors extended by a σ–bond framework, such as a dichalcogenolane ring, a dichalcogenane ring, and an alkyl group, is described.  Although these appended σ–bond frameworks cannot participate in electrical conduction, several of the resulting TTF donors produce organic metals, some of which retain the metallic conductivity down to low temperatures.  In addition, a new donor packing motif with two-dimensional interaction occurs with the use of a dioxolane-linked TTF donor.