The single ionization and dissociation of ethanol molecules induced by low-energy electrons (E0 = 90 eV) are investigated using multiparticle coincident momentum spectroscopy. By detecting two outgoing electrons (e1 and e2) and one fragment ion in coincidence, we obtain the energy deposition (E0 − E1 − E2) during electron ionization of the molecule, i.e., the binding energy spectra, for production of the different ionic fragments C2H5OH+, C2H4OH+, COH+, and H3O+. These data allow us to study the ionization channels for different ionic products. In particular, we focus on H3O+ as a product of double hydrogen migration. It is found that this channel mainly originates from the ionization of outer-valance orbitals (3a″,10a′, 2a″, 9a′, 8a′, 1a″, and 7a′). Additionally, there are minor contributions from the inner-valence orbitals such as 6a′, 5a′, and 4a′. Quantum chemistry calculations show two fragmentation pathways: concerted and sequential processes for formation of H3O+.