Photoionization cross sections and partial ion yields of Xe and XeF_2 from Xe 3d_{5/2}, Xe 3d_{3/2}, and F 1s subshells in the 660--740 eV range are compared to explore effects of the F ligands. The Xe 3d - \epsilonf continuum shape resonances dominate the photoionization cross sections of both the atom and molecule, but prominent resonances appear in the XeF_2 cross section due to nominal excitation of Xe 3d and F 1s electrons to the lowest unoccupied molecular orbital (LUMO), a delocalized anti-bonding MO. The subshell ionization thresholds, the LUMO resonance energies and their oscillator strengths are calculated by relativistic coupled-cluster methods. Several charge states and fragment ions are produced from the atom and molecule due to alternative decay pathways from the inner-shell holes. Total and partial ion yields vary in response to the shape resonances and LUMO resonances. Previous calculations and measurements of atomic Xe 3d core-hole decay channels and our calculated results for XeF_2 guide interpretations of the molecular ion products. The partial ion yields of XeF_2 are dominated by Xe 3d core-hole decays, but distinct ion products are measured at the F 1s - LUMO resonance. Xe 3d core-hole decays from XeF_2 produce lower charge states in comparison with atomic Xe, and energetic F ions are produced by Coulomb explosions of the molecular ions. The measurements support a model of molecular core-hole decay that begins with a localized hole, stepwise Auger electron emission spreads charge across neighboring atoms, and the system fragments energetically.