Phenylacetylene is a molecule of interest because of its role in the chemistry of combustion. It has also been discovered to have some unique photophysical properties. When excited to a single rotational level of its lowest singlet state in a collisionless environment, it rapidly chooses either to become a species (probably an isomer) that lives for at least hundreds of microseconds, or stays in the excited singlet state to fluoresce. Both the longevity of its photoproduct and the bifurcation of its excited state evolution pathway are properties previously unseen in the photophysics of aromatic molecules. This molecule has been studied using excitation with an ultra-high resolution laser, combined with excited state photoelectron spectroscopy. Possibilities for its anomalous behavior will be discussed.