The beneficial effect on the dehydrogenation of ammonia borane due to mixing with hydrophobic ionic liquids (ILs) is investigated by means of detailed combined TG–DTA and IR measurements. Desorption of several mixtures of ammonia borane with hydrophobic ILs having bis(trifluoromethanesulfonyl)-imide or trifluorosulfonyl-imide anions was studied in both isothermal and non-isothermal conditions. The addition of hydrophobic liquids lowers the dehydrogenation temperatures and allows the observation of the decomposition process without any induction time even at temperatures below 90 °C. The IR data of the products of the decomposition confirm that ILs do not react with AB but provide an highly polar medium which promotes the decomposition reaction. Furthermore, the proposed method to enhance hydrogen release from ammonia borane provides the possibility of working in air avoiding any protective atmosphere.