Combustion characteristics of natural gas and dimethyl ether (DME) mixture in a homogeneous charge compression ignition (HCCI) engine were studied numerically. Detailed chemical kinetics with 83 species and 360 reactions was used with an engine CFD code to simulate the combustion process. Operating conditions with different fuel compositions were simulated. Combustion, nitrogen oxides emissions and effects of fuel compositions on engine operating limits were well predicted by the present model. Chemical kinetics analysis indicated that ignition was achieved by DME oxidation which, in turn, induced combustion of natural gas. Low-temperature heat release is more pronounced as the amount of DME increases. Engine operations become unstable as the excess air ratio of natural gas is reduced near 2. The model also captures the HCCI features of low-combustion temperature and low-nitrogen oxides emissions for the alternative fuels used in this study. (c) 2006 Elsevier Ltd. All rights reserved.