Polycyclic aromatic hydrocarbons are major species in astrophysical environments, and this motivates their study in samples of astrochemical interest such as meteorites and laboratory analogues of stardust. Molecular analyses of carbonaceous matter in these samples show a dominant peak at m/z = 202.078 corresponding to C16H10. Obtaining information on the associated isomeric structures is a challenge for the molecular analysis of samples available in very small quantities (mg or less). Here we show that coupling laser desorption ionization mass spectrometry with ion trapping opens up the possibility of unraveling isomers by activating ion fragmentation via collisions or photon absorption. We report the best criteria for differentiating isomers with comparable dissociation energies, namely pyrene, fluoranthene, and 9-ethynylphenanthrene, on the basis of the parent dissociation curve and the ratio of dehydrogenation channels. Photoabsorption schemes (multiple photon absorption in the visible range and single photon absorption at 10.5 eV) are more effective in differentiating these isomers than activation by low energy collisions. The impact of the activation scheme on the fragmentation kinetics and dehydrogenation pathways is discussed. By analyzing the 10.5 eV photodissociation measurements with a simple kinetic model, we were able to derive a branching ratio for the H and 2H/H2 loss channels of the parent ions. The results suggest a role in the formation of H2 for bay hydrogens that are present in both fluoranthene and 9-ethynylphenanthrene. In addition, we suggest for the latter the presence of a highly competitive 2H loss channel, possibly associated with the formation of a pentagonal ring.