In this contribution, we investigated the photo-induced EDPT process in isolated PrdPyr-MeOH complexes by means of ab initio electronic-structure and nonadiabatic molecular dynamics calculations. We found that the methanol molecule acts as a proton-donor in the hydrogen-bonded complex with PrdPyr, adopting perpendicular orientation with respect to the aromatic plane. Three stable structures differing by the nitrogen atom acting as the proton-acceptor were identified. Upon photo-excitation to the lowest-energy bright state, S 2 (ππ * ), all systems undergo rapid relaxation, firstly to S 1 (nπ * ) and, subsequently, to the S 0 state. The rate of the process is visibly higher when the hydrogen bond is formed with one of the neighbouring N atoms and not with the single nitrogen of the pyrazine ring. This effect is rationalized by interaction between the methanol oxygen and the neighboring nitrogen atom, not directly involved in the HB formation. Our findings point to beneficial effect of the βposition arrangement of electronegative centers for photo-oxidation reactions, providing further clues for future design of efficient organic catalysts for water splitting applications.