Ab initio electron propagator methods are applied to the prediction, assignment, and interpretation of the valence photoelectron spectra of free base porphine and of magnesium and zinc porphyrins. Tests of various approximate self-energies, including the partial third (P3), the outer valence Green's function, and the nondiagonal, renormalized second-order (NR2) methods are performed. Basis set effects and reduced active orbital spaces are examined as well. The P3 method and the one-electron picture of ionization that accompanies it are validated for the first two cationic states and for states with a holes that are localized in nitrogen, lone pair regions. In the remaining pi-hole states, there is significant shake-up character and NR2 results provide useful diagnostics of correlation effects.