Abstract. Here we report the electronic structure of praseodymium filled skutterudite compound PrOs 4 Sb 12 . The theoretical photoemission spectrum (PES) at ћω = 21.2 eV shows four distinct structures peaking at about -0.2, -7.7, -13.7 and -18.2 eV. But on increasing the photon energy to 40.8 eV, the peak at -0.2 eV becomes a prominent or pronounced peak, the peak at -7.7 eV decreases in intensity, the peak at -13.7 eV increases intensity, the peak at -18.2 eV reduces in intensity and another peak emerges. These structures are interpreted to be associated with the density-of-states features on the basis of the results of band structure calculation. Hence, the peak at -0.2 eV arises from the symmetry point P at -11.61 eV, the peak at -7.7 eV comes from the symmetry point P at -11.62 eV, the peak at -13.7 eV arises from the symmetry point P at -11.88 eV and the peak at -18.2 eV arises from the symmetry point P at -11.88 eV. The PES energy level difference for PrOs 4 Sb 12 fell within the range -0.5 to -7.5 eV indicating that it can be used in designing electronic devices. The energies of specific electronic states in the band structure of PrOs 4 Sb 12 showed that it could be used for the development of solid-state devices.