In this study, the effect of the SOC in third-row transition metal hexafluorides is extensively investigated. The multi-reference configuration-interaction (MRCI) method based on the exact two-component Hamiltonian is employed to calculate the structures and vertical excited energies. The calculated electronic excited states, including the SOC, are assigned based on the double group, which is a relativistic group symmetry, taking the SOC into account. The schematic diagrams based on the one-electron orbital Figure are also proposed.