We investigate the electronic and magnetic properties of the synthesized double perovskites and , using density functional calculations, crystal field theory, superexchange pictures, and Monte Carlo simulations. We find that both systems are antiferromagnetic (AFM) Mott insulators, with the high-spin () and the low-spin () configurations. We address that their lattice distortion induces orbital mixing and thus enables the normal charge excitation with the electron hopping from the Ir ‘’ to Ni ‘’ orbitals, which promotes the AFM coupling. Therefore, the increasing mixing accounts for the enhanced from the less distorted to the more distorted . Moreover, our test calculations find that in the otherwise ideally cubic , the charge excitation is forbidden, and only the abnormal excitation gives a weakly ferromagnetic behavior. Furthermore, we find that, owing to the crystal field splitting, Hund exchange, and broad band formation in the highly coordinated fcc sublattice, ions are not in the state but in the state carrying a finite orbital moment by spin-orbit coupling. This paper clarifies the varying magnetism in and associated with the lattice distortions.