The direct influence of hydrogen-bonding on chemical reactivity within [{NO}(n){CH3CH2OH}(m)](+) ions is presented in this study. At high ethanol concentrations in the ethanol/NO gas mixture, the primary ion-molecule reaction generates CH3CH2ONO and HNO via loss of a hydrogen solely from the hydroxy group of the ethanol This behavior continues without regard to the ethanol concentration until a certain critical value of the ethanol concentration is reached. Further decreasing the ethanol composition gives rise to a;change in the position of the hydrogen atom loss, from the hydroxyl group to the methylene group. These results, we believe, originate from structural changes in the hydrogen-bonding network of the ethanols. We propose a model to account for this distinctive chemistry within NO/ethanol clusters and have interpreted the difference in the chemical reactivity between NO/ethanol and NO/methanol in terms of geometrical versus energetic factors.