High resolution x-ray fluorescence spectra have been recorded for emission in different directions from a single crystal of the compound [Rh(en)(3)][Mn(N)(CN)(5)].H2O. The spectra are interpreted by comparison with density functional theory (DFT) electronic structure calculations. The Kbeta(') line, which is strongly polarized along the Mn-N axis, can be viewed as an N(2s)-->Mn(1s) transition, and the angular dependence is understood within the dipole approximation. The so-called Kbeta(2,5) region has numerous contributions but is dominated by Mn(4p) and C(2s)-->Mn(1s) transitions. Transition energy splittings are found in agreement with those of calculated occupied molecular orbitals to within 1 eV. Computed relative transition probabilities reproduce experimentally observed trends.