The reaction dynamics of H₂COO to form HCOOH and dioxirane as first steps for OH-elimination is quantitatively investigated. Using a machine learned potential energy surface (PES) at the CASPT2/aug-cc-pVTZ level of theory vibrational excitation along the CH-normal mode ν_CH with energies up to 40.0 kcal mol⁻¹ (∼5ν_CH) leads almost exclusively to HCOOH which further decomposes into OH + HCO. Although the barrier to form dioxirane is only 21.4 kcal mol⁻¹ the reaction probability to form dioxirane is two orders of magnitude lower if the CH-stretch mode is excited. Following the dioxirane-formation pathway is facile, however, if the COO-bend vibration is excited together with energies equivalent to ∼2ν_CH or ∼3ν_COO. For OH-formation in the atmosphere the pathway through HCOOH is probably most relevant because the alternative pathways (through dioxirane or formic acid) involve several intermediates that can de-excite through collisions, relax via internal vibrational relaxation (IVR), or pass through loose and vulnerable transition states (formic acid). This work demonstrates how, by selectively exciting particular vibrational modes, it is possible to dial into desired reaction channels with a high degree of specificity.