Laser multiphoton dissociation–resonance-enhanced multiphoton ionization (MPD–REMPI) and time-of-flight photoelectron spectra (TOF-PES) of Fe(C5H5)2, Co(C5H5)2, and Ni(C5H5)2 have been obtained in the range 380–390 nm, and the MPD–REMPI of Fe(C5H5)2 and Co(C5H5)2 have been obtained in the range 445–455 nm. The only ions produced by the pulsed dye laser are Fe+, Co+, and Ni+. Transitions observed in the MPD–REMPI spectra are assigned to resonant states of the neutral atoms. Final states of the atomic ions are determined from the TOF-PES spectra. For Ni and Co, there appears to be a propensity for core preservation of the resonant state upon ionization if the resonant state has an electron configuration with an electron in a d-type Rydberg orbital. For Fe, no such propensity is observed.