Two small combustion systems, methyl hydroperoxide (CH3OOH) and 2-propanol ((CH3)2CHOH), were studied using imaging photoelectron photoion coincidence spectroscopy (iPEPICO), which combines photoelectron spectroscopy and photoionization mass spectrometry to detect coincident photoelectron-photoion pairs. In the photon energy range of 11.4–14.0 eV, energy selected CH3OOH+ ions dissociate into CH2OOH+, HCO+, CH3+, and H3O+ ions. The lowest-energy dissociation channel is the formation of the cation of the smallest “QOOH” radical, CH2OOH+. A statistical rate model fitted to the experimental data yields a 0 K appearance energy of 11.647 ± 0.005 eV for the CH2OOH+ ion, and a 74.2 ± 2.6 kJ mol–1 mixed experimental-theoretical 0 K heat of formation for the CH2OOH radical. The proton affinity of the Criegee intermediate, CH2OO, was also obtained from the heat of formation of CH2OOH+ (792.8 ± 0.9 kJ mol–1) to be 847.7 ± 1.1 kJ mol–1, reducing the uncertainty of the previously available computational value by a factor of 4. RRKM modeling of the higher-energy fragmentation processes, supported by Born–Oppenheimer molecular dynamics simulations, found that the HCO+ fragment ion is produced through a roaming transition state; H3O+ is formed in a consecutive process from the CH2OOH+ fragment ion; and direct C–O fission of the molecular ion leads to the methyl cation. Experimentally, 2-propanol has been found to dissociate primarily into CH2CHOH+, CH3CHOH+, CH3CHCH3+, and, as a minor product, into (CH3)2COH+ ions within a photon energy range of 10.0–13.1eV. There are interesting dissociation dynamics involving breaking the C–¬C bond: the lowest energy product (CH3 loss) is quickly outcompeted by a kinetically favored CH4 loss. At low internal energies of < 0.3 eV, the loss of CH4 dominates through a roaming pathway, when the leaving CH3 abstracts a hydrogen atom from the other methyl group. At higher energy, the direct loss of CH3• quickly takes over as its transition state is much less tight and, thus, it is kinetically favored. The statistical model fitted to the experimental data yielded the appearance energy corresponding to the thermochemical limit for the CH3-loss dissociation and the 0 K heats of formation of the CH3CHOH+ ion was found to be in good agreement with ATcT values and with our previous study on ethanol.