With the advantages of ultra-low emissions of oxides of nitrogen (NOX) and high thermal efficiency, the homogeneous charge compression ignition (HCCI) mode applied to marine diesel engine is expected to be one of the technical solutions to meet the International Maritime Organization (IMO) MARPOL73/78 Convention-Annex VI Amendment Tier III requirement. According to the NOX chemical reaction mechanism, taking a marine diesel engine as the application object, the numerical study on the NOX formation characteristics of n-heptane for HCCI combustion process is performed. The results indicate that NO is usually the main component in the generation and emissions of NOX with the n-heptane HCCI mode. The combustor temperature plays more important role in the proportion of NO generation and emission. Compared with the experimental data of conventional marine diesel engine, the emission reduction rate of NOX can achieve an average of more than 95% in using HCCI technology.