The formation and structure of dicobalt tetroxide (Co2O4) has been investigated using matrix isolation in solid neon and argon coupled to infrared spectroscopy and quantum chemical methods. It is found that Co2O4 can be formed by dimerization of cobalt dioxide without activation energy by diffusion of ground state CoO2, molecules at 9 K in the dark. The IR data on eight fundamentals, isotopic effects and quantum chemical calculations are both consistent with a centro-symmetrical structure with two pairs of equivalent oxygen atoms, engaged in a stronger terminal Co-O bond and in a weaker bridging Co-O-Co position. Evidence for other, metastable states is also presented, but the data are not conclusive. The electronic structure and formation pathway has been investigated using the Tao-Perdew-Staroverov-Scuseria/triple-zeta valence polarived basis set (TPSS/TZVP) and broken symmetry unrestricted density functional theory (BS-UDFT) approach and the ground electronic state is predicted to be an open shell (1)A(g) singlet with the quintet, triplet, septet, and nonet states above by 3.3, 4.9, 9.3, and 27.7 kcal/mol, respectively, but certainly has a complex multireference character that hinders the use of more precise multireference approaches. Different formation pathways have been considered, and the 2(O=Co=O) -> Co2O4 dimerization reaction is found to be the only barrierless channel and to be strongly exothermic. Comparisons with another transition metal (TM) oxide system (V2O4) suggests that the difference in predicted ground state geometries in TM2O4 systems might be due in HOMO-LUMO shapes of the isolated dioxide subunits and optimal overlap configurations.