The direct and resonant single-photon photoionization of W63+ ions from their ground state 1s
22s
22p
63s
2
S
1/2 and four lowly-excited states 1s
22s
22p
63p
2
P
1/2,3/2 and 1s
22s
22p
63d
2
D
3/2,5/2 has been studied within the framework of the relativistic R-matrix method and the multiconfigurational Dirac–Fock method. Special attention has been paid to obtaining direct and resonant ionization limits and to identifying possible resonant symmetries of W63+ ions. To this end, the photoionization cross-sections have been calculated using the Dirac Atomic R-matrix Code package. Direct and resonant ionization limits were obtained for the ground-state photoionization of W63+ ions, and the resonant peaks identified were found to be associated with the resonances 1s
22s
22p
53lnl′ and 1s
22s2p
63lnl′ (l, l′ = s, p, d) for the fine-structured energy level or configuration at the level of fine structure or configuration. For excited-state photoionization, however, the resonant ionization limits and resonant peaks were hardly distinguishable due to much more densely spaced resonant peaks and a complicated resonant structure, although the respective direct ionization limits are obtained. We expect that this work will remedy the current lack of fundamental studies of the photoionization of W63+ ions and be helpful in the diagnosis and simulation of fusion plasmas in conjunction with the available photoionization data for tungsten ions in other charge states.