Photoelectron spectra of molecular WF₆ have been recorded with photons in the energy range 22-90 eV using synchrotron radiation. In addition to the previously observed valence orbitals, the F 2s and W 4f and 5p core levels have been observed and their ionisation energies compared with available MS X alpha and relativistic Dirac-Slater quantum mechanical calculations. Branching ratios have been calculated for all orbitals in order to gain an insight into their localisation properties. Selective enhancement of the branching ratios of the 2a_1g+1t_2g and 2t_1u orbitals has been observed and attributed to autoionisation including a 5p-5d resonance in tungsten. Strong shape resonance effects produce enhancements in branching ratios for the 3t_1u+1t_2u and 2e_g orbitals.