The synthesis and structural characterization of racemic and enantiopure tetrathiafulvalene-oxazolines (TTF-OX) derivatives, with an emphasis on several key features, are reviewed. These compounds can serve as precursors for conducting chiral materials, but also as electroactive ligands for transition metal complexes. Crystalline conducting molecular materials have been obtained uponelectrocrystallization of some of the donors, such as the first complete series of mixed-valence metallic salts based on chiral tetrathiafulvalenes, bearing the (R)-, (S)-, or racemic (±)-methyl–oxazoline heterocycle and the AsF6– monoanion. Transition metal complexes containing electroactive TTF-OX ligands have been prepared as well. Palladium and iridium complexes containing TTF-phosphino-oxazoline (TTF-PHOX) ligands have been applied in two homogeneous catalytic processes.