The ion conversion processes in CH2Cl2-enhanced vacuum ultraviolet photoionization of oxygenated volatile organic compounds (OVOCs) have been systematically studied by regulating the pressure, humidity, and reaction time in the ionization source of a time-of-flight mass spectrometer. As the ionization source pressure increased from 100 to 1100 Pa, the main characteristic ions changed from CH2Cl+ to CH2Cl+(H2O), CH2OH+, and C2H4OH+ and then to the hydrated hydronium ions H3O+(H2O)n (n = 1, 2, 3). The total ion current (TIC) almost remained unchanged even if the humidity increased from 44 to 3120 ppmv, indicating interconversion between ions through ion-molecule reactions. The intensity of protonated methanol/ethanol (sample S) ion was almost linearly correlated with the intensity of H3O+(H2O)n, which pointed to the proton transfer reaction (PTR) mechanism. The reaction time was regulated by the electric field strength in the ionization region. The intensity variation trends of different ions with the reaction time indicated that a series of step-by-step ion-molecule reactions occurred in the ionization source, i.e., the primary ion CH2Cl+ reacted with H2O and converted to the intermediate product ions CH2OH+ and C2H4OH+, which then further reacted with H2O and led to the production of H3O+, and finally, the protonated sample ion SH+ was obtained through PTR with H3O+, as the ion-molecule reactions progressed. This study provides valuable insights into understanding the formation mechanism of some unexpected intermediate product ions and hydrated hydronium ions in dopant-enhanced VUV photoionization and also helps to optimize experimental conditions to enhance the sensitivity of OVOCs.