In this paper we report the results of an experimental study of collision-free molecular multiphoton dissociation (MPD) and molecular multiphoton ionization (MPI) of nickelocene (NiC 10H 10), induced by the light of a tunable dye laser in the wavelength region 3750–5200 A. The spectral dependence of the ion signal reveals a multitude of narrow (fwhm from <0.5 cm −1 to 1.5 cm −1) intense peaks superimposed on a very weak background (relative amplitude ratio for peaks/background ≈ 10 3). The sharp resonances in the ion signal are attributed, on the basis of spectroscopic analysis, to two-photon resonant three-photon ionization of Ni(I) and to one-photon resonant three-photon ionization of Ni(I), the Ni(I) being produced by MPD of nickelocene. The ion signal in the spectral range 3750–3950 A reveals enhanced continuous background due to MPI of nickelocene. This ion signal spectra, together with studies of the intensity dependence of the overall (nickelocene MPD) - (Ni(I) MPI) processes, as well as the (nickelocene molecular MPI) reaction, reveal four reactive processes. (a) Two-photon molecular MPI for hω ⩾ 3.10 eV photons. (b) Three-photon molecular MPI for hω = 3.10-2.10 eV. (c) Two-photon MPD at hω ⩾ 2.86 eV. (d) Three-photon MPD for hω = 2.8-1.9 eV. The overall dissociation energy of nickelocene (Nicp 2) to give Ni + 2cp was determined to be 5.76 ± 0.60 eV and the two-photon ionization potential of this molecule is 6.29 ± 0.015 eV. Our results provide dynamic evidence concerning a simultaneous “explosive” photodissociation mechanism of Nicp 2 by process (c) and for the dominating role of the dissociative channel, characterized by a branching ratio of ⩾50 in favor of predissociation over autoionization, for process (c) at 6.3–6.6 eV. The MPD processes (c) and (d) are expected to exhibit intramolecular erosion of phase coherence effects. Processes (c) and (d) are of high efficiency ≈0.01 ions/molecule at saturation exhibited at laser power of ≈ 10 8 W cm −2.