Ammonia (NH3) is a promising hydrogen carrier that effectively connects producers of blue hydrogen with consumers, giving rapid conversion of ammonia to hydrogen a critical role in utilizing hydrogen at the endpoints of application in an ammonia-hydrogen economy. Because conventional thermal cracking of NH3 is an energy intensive process, requiring a relatively longer cold start duration, plasma technology is being considered as an assisting tool—or an alternative. Here we detail how an NH3 cracking process, using a microwave plasma jet (MWPJ) under atmospheric pressure, was governed by thermal decomposition reactions. We found that a delivered MW energy density (ED) captured the conversion of NH3 well, showing a full conversion for ED > 6 kJ l−1 with 0.5-% v/v NH3 in an argon flow. The hydrogen production rate displayed a linear increase with MW power and the NH3 content, being almost independent of a total flow rate. A simplified one-dimensional numerical model, adopting a thermal NH3 decomposition mechanism, predicted the experimental data well, indicating the importance of thermal decomposition in the plasma chemistry. We believe that such a prompt thermal reaction, caused by MW plasma, will facilitate a mobile and/or non-steady application. A process combined with the conventional catalytic method should also effectively solve a cold start issue.