Two dicobalt compounds containing Co–Co bonds with DAniF ligands (DAniF = N,N′-di-p-anisylformamidinate) were synthesized and characterized by X-ray crystallography. One has a typical tetragonal paddlewheel structure, Co2(DAniF)4 (1), while the other one has a rare trigonal paddlewheel structure with three formamidinate ligands spanning a low oxidation state in the Co 2 3+ unit in Co2(DAniF)3 (2). The singly bonded Co–Co distance in the Co 2 4+ unit in 1 is 2.3580(16) Å while the Co–Co bond distance in 2 is 2.3773(5) Å. The average torsion angles are 10.46° and 2.34° for 1 and 2, respectively. Compound 1 is diamagnetic but 2 is paramagnetic as shown by the 1H NMR spectra.