Skutterudites, with rattler atoms introduced in voids in the crystal unit cell, are promising thermoelectric materials. We modify the binary skutterudite with atomic content Co(8)P(24) in the cubic crystal unit cell by adding La as rattlers in all available voids and replacing Co by Fe to maintain charge balance, resulting in La(2)Fe(8)P(24). The intention is to leave the electronic structure unaltered while decreasing the thermal conductivity due to the presence of the rattlers. We compare the electronic structure of these two compounds by studying the L-edges of P and of the transition elements Co and Fe using electron energy loss spectroscopy (EELS). Our studies of the transition metal white lines show that the 3d electron count is similar for Co and Fe in these compounds. As elemental Fe has one electron less than Co, this supports the notion that each La atom donates three electrons. The L-edges of P in these two skutterudites are quite similar, signalling only minor differences in electronic structure. This is in reasonable agreement with density functional theory (DFT) calculations, and with our multiple scattering FEFF calculations of the near edge structure. However, our experimental plasmon energies and dielectric functions deviate considerably from predictions based on DFT calculations.