Density functional theory (DFT) represents a unified framework for gaining molecular level insight into molybdenum–iron (MoFe) nitrogenase. However, accurately describing the electronic structure of the spin-polarized and spin-coupled iron–molybdenum cofactor (FeMo-co) where N2 reduction occurs within MoFe nitrogenase is challenging. Therefore, the enhancement of DFT to include broken symmetry (BS-DFT) plus approximate spin projection has proven valuable because it provides a procedure to compute reliable geometries, energies, redox potentials, and quantities relevant to M?ssbauer and ENDOR spectroscopies. After describing the theoretical tools necessary to obtain this information, we show by way of examples how BS-DFT is a very powerful partner to experiment. We expect that quantitative quantum chemical theory of this type will play an ever-increasing role in helping to decipher complex bioinorganic systems like those found in MoFe nitrogenase.