Transition-metal cation complexes with 1,3,5,7-cyclooctatetraene of the form M+(C8H8)(1,2) (M = V, Fe, Ni, and Ag) are produced by laser vaporization in a pulsed nozzle cluster source. The clusters are mass-selected and photodissociated using the second and third harmonics of an Nd:YAG laser (532 and 355 nm). The first-row transition-metal complexes undergo retro-cyclotrimerization to produce M+(benzene). The photo-dissociation of V+(C8H8) also produces a significant amount of V+(C5H5). This is attributed to the ability of V+ to donate electron density to stabilize a cyclopentadienyl anion. Dissociation of Ag+(C8H8) exhibits a photoinduced charge-transfer pathway allowing an upper limit of 2.6 eV to be placed on the binding energy in this system. Complexes with two C8H8 molecules primarily dissociate by loss of intact C8H8 molecules with some fragmentation to M+(C10H10) for M+ = V and Fe. Fragmentation of these M+(C10H10) species indicates a structure that is not ferrocene-like in nature. Mixed sandwich complexes are produced with both COT and benzene as ligands, and these dissociate by eliminating benzene, indicating that COT is more strongly bound to these transition-metal ions. The results of these experiments shed new insight on the bonding and photochemistry of these organometallic systems.