The electronic structure of Nd2Fe14B has been calculated using the first‐principle orthogonalized linear combination of atomic orbitals method. The f electrons in Nd are included in the calculation but are treated as localized states in the determination of the Fermi energy. Results are presented for the total density of states (DOS), orbital‐decomposed, and spin‐decomposed partial DOS. The calculated spin‐magnetic moments on each of the six Fe sites are in good agreement with the values deduced from the neutron scattering experiment. The charge density map and the spin density map on the basal plane of the tetragonal cell show the evidence for covalent bonding between Fe and B atoms and reveal the distortion from the spherically symmetric distribution around the atomic sites.