The ionization dynamics (iron ion and neutral atom absolute line densities) produced in the KrF excimer laser ablation of iron and a laser‐ablation‐assisted plasma discharge (LAAPD) ion source have been characterized by a new dye‐laser‐based resonant ultraviolet interferometry diagnostic. The ablated material is produced by focusing a KrF excimer laser (248 nm,<1 J, 40 ns) onto a solid iron target. The LAAPD ion source configuration employs an annular electrode in front of the grounded target. Simultaneous to the excimer laser striking the target, a three‐element, inductor–capacitor, pulse‐forming network is discharged across the electrode–target gap. Peak discharge parameters of 3600 V and 680 A yield a peak discharge power of 1.3 MW through the laser ablation plume. Iron neutral atom line densities are measured by tuning the dye laser near the 271.903 nm (a 5D–y 5P0) ground‐state and 273.358 nm (a 5F–w 5D0) excited‐state transitions while iron singly ionized line densities are measured using the 263.105 nm (a 6D–z 6D0) and 273.955 nm (a 4D–z 4D0) excited‐state transitions. The line density, expansion velocity, temperature, and number of each species have been characterized as a function of time for laser ablation and the LAAPD. Data analysis assuming a Boltzmann distribution yields the ionization ratio (ni/nn) and indicates that the laser ablation plume is substantially ionized. With application of the discharge, neutral iron atoms are depleted from the plume, while iron ions are created, resulting in a factor of ∼5 increase in the plume ionization ratio. Species temperatures range from 0.5 to 1.0 eV while ion line densities in excess of 1×1015cm−2have been measured, implying peak ion densities of ∼1×1015cm−3. ©1996 American Institute of Physics.