We present femtosecond pump-probe photoionization experiments with indium dimers (In2) solvated in helium nanodroplets (HeN). At short pump-probe time delays, where the excited In2* is still located inside the droplet, we surprisingly observe detachment of InHen+ ions with n = 1 to ∼30 from the droplet. These ions indicate that fragmentation of In2 occurs and that the kinetic energy release enables In+ to overcome the attractive HeN potential, which typically prevents ion ejection from the droplet. We find that the transient InHen+ signal reveals vibrational wave packet motion in neutral In2*. By correlating the InHen+ signal with the corresponding photoelectrons through covariance detection, we unequivocally identify the ionization pathway leading to InHen+: pump-excitation from the ground-state In2 creates a vibrational wave packet in In2*, followed by probe-ionization to the cationic ground state In2+. Subsequently, a further probe photon promotes the molecule to an excited ionic state In2+* of nonbonding character, leading to fragmentation and kinetic energy release. This interpretation is additionally supported by probe power- and droplet-size dependencies, as well as energetic considerations. Unambiguous assignment of the ionization path to absorption-ionization-dissociation (fragmentation of the ion) in contrast to absorption-dissociation-ionization (fragmentation of the neutral) is enabled by ion ejection and electron-ion correlation. This complementary observable for ultrafast photochemical processes inside HeN will be particularly valuable for more complex systems.