Phthalide pyrolysis has been assumed to be a clean fulvenallene source. We show that this is only true at low temperatures, and the C7H6 isomers 1-, 2-, and 5-ethynylcyclopentadiene are also formed at high pyrolysis temperatures. Photoion mass-selected threshold photoelectron spectra are analyzed with the help of (time-dependent) density functional theory, (TD-)DFT, and equation-of-motion ionization potential coupled cluster, EOM-IP-CCSD, calculations, as well as Franck-Condon simulations of partly overlapping bands, to determine ionization energies. The fulvenallene ionization energy is confirmed at 8.23 +/- 0.01 eV, and the ionization energies of 1-, 2 and S-ethynylcyclopentadiene are newly determined at 8.27 +/- 0.01, 8.49 +/- 0.01 and 8.76 +/- 0.02 eV, respectively. Excited state features in the photoelectron spectrum, in particular the (A) over tilde+ (2)A' band of 1-ethynylcyclopentadiene, are shown to be practical to isomer-selectively detect species when the ground-state band is congested. At high pyrolysis temperatures, the C7H6 isomers may lose a hydrogen atom and yield the fulvenallenyl radical. Its ionization energy is confirmed at 8.20 +/- 0.01 eV. The vibrational fingerprint of the first triplet fulvenallenyl cation state is also revealed and yields an ionization energy of 8.33 +/- 0.02 eV. Further triplet cation states are identified and modeled in the 10-11 eV range. A reaction mechanism is proposed based on potential energy surface calculations. Based on a simplified reactor model, we show that the C7H6 isomer distribution is far from thermal equilibrium in the reactor, presumably because irreversible H loss competes efficiently with isomerization.