The potential use of hydrogen peroxide as an ignition promoter to enable the use of ammonia in compression ignition engines is explored in the current study. A simplified numerical HCCI engine model within the Chemkin Pro suite is employed. The numerical investigation reveals that the proposed use of hydrogen peroxide is significantly more advantageous against the more conventional method of preheating the intake charge to achieve ignition, whilst using a glow plug. In particular, the IMEP, power and torque exhibit an increase greater than 65% along with a spectacular decrease of NOx emissions reaching in certain cases a 9-fold decrease. The thermal efficiency exhibits a more moderate, yet non-negligible increase, around 5%. Generally, the incremental increase of hydrogen peroxide leads to the increase of the IMEP, power and torque as well as the maximum temperature and, hence, NOx emissions. These increases are largely linear with the hydrogen peroxide addition. Finally, the introduction of hydrogen peroxide leads to a two-stage ignition process, where the first ignition stage was found to be instrumental to the control of the ignition process, and, therefore, the system’s efficiency. Further research is required to substantiate further the feasibility and the the limitations of the proposed technology which can enable the rapid decarbonization of heavy duty applications, such as marine ships and trucks.