Tunable laser photodissociation spectroscopy in the 700-400 nm region and photofragment imaging experiments are employed to investigate the Fe+(acetylene) ion-molecule complex. At energies above a threshold at 679 nm, continuous dissociation is detected throughout the visible wavelength region, with regions of broad structure. Comparison to the spectrum predicted by time-dependent density functional theory (TD-DFT) indicates that the complex has a quartet ground state. The dissociation threshold for Fe+(acetylene) at 679 nm provides the dissociation energy on the quartet potential energy surface. Correction for the atomic quartet-sextet spin state energy difference provides an adiabatic dissociation energy of 36.8 ± 0.2 kcal/mol. Photofragment imaging of the Fe+ photoproduct produced at 603.5 nm produces significant kinetic energy release (KER). The photon energy and the maximum value of the KER provide an upper limit on the dissociation energy of D0 ≤ 34.6 ± 3.2 kcal/mol. The dissociation energies determined from the spectroscopy and photofragment imaging experiments agree nicely with the value determined previously by collision-induced dissociation (38.0 ± 2.6 kcal/mol). However, both values are significantly lower than those produced by computational chemistry at the DFT level using different functionals recommended for transition-metal chemistry.