Isopropanol (2-propanol) dissociatively photoionizes primarily into the CH₂CHOH⁺, CH₃CHOH⁺, CH₃CHCH₃⁺ fragment ions, and, as a minor product, into (CH₃)₂COH⁺ in the 10.0–13.1 eV photon energy range as shown by Imaging Photoelectron Photoion Coincidence (iPEPICO) spectroscopy. At internal energies of below 0.3 eV, the loss of CH₄ dominates via a roaming pathway, in which the leaving CH₃ abstracts a hydrogen atom from the other methyl group. At higher energies, the kinetically favored direct loss of a methyl radical quickly takes over as its transition state is looser. We use the measured CH₃-loss appearance energy of 10.44 ± 0.01 eV to confirm the heat of formation of protonated acetaldehyde, CH₃CHOH⁺, as Δ_fH° = 608 ± 1 kJ mol⁻¹ at 0 K. The highest-energy dissociation observed leads to CH₃CHCH₃⁺ + OH, which corresponds to C–O bond scission. This process is the premier example of a non-statistical dissociation which can be modeled using a statistical model, albeit with a physically meaningless appearance energy. This channel is shown to be non-statistical due to preferential OH loss from the first electronically excited ion state.