Communication: Extended TTF-based donor systems based for the first time on selenophene (see Fig.) are reported. Selenophene is an isologue of thiophene but has a stronger electron-donating ability, a larger size, and a higher polarizability. These factors should lead to materials with increased bandwidth, improved dimensionality, increased electrical conductivity, and reduced on-site Coulombic repulsion. The one-pot synthesis of these materials and their complexation with TCNQ are presented.