Unveiling reaction mechanisms by isomer‐selective detection of reactive intermediates requires advanced spectroscopic knowledge. We study the photoionization of fulvenone (c-C₅H₄=C=O), a reactive ketene species relevant in catalytic pyrolysis of lignin, which was generated by pyrolysis of 2‐methoxy acetophenone. The highresolution threshold photoelectron spectrum (TPES) with vacuum ultraviolet synchrotron radiation revealed well‐resolved vibrational transitions, assigned to ring deformation modes of the cyclopentadienyl moiety. The adiabatic ionization energy was determined to be 8.25 ± 0.01 eV and is assigned to the X^~+2A₂ ← X^~1A₁ transition. A broad and featureless band arising at 9 eV is associated with the A^~+ 2B₁ ← X^~1A₁ excitation. A conical intersection is responsible for the ultrafast relaxation of the fulvenone cation from the A^~+ into the X^~+ state resulting in a featureless and lifetime broadened band. These insights will increase the detection capabilities for fulvenone and thereby help to elucidate reaction mechanisms in lignin catalytic pyrolysis