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Hydrogen is expected to be a clean and energy-efficient fuel for the next generation of power sources because it is CO2-free and has excellent combustion characteristics. In this study, an attempt was made to apply Homogeneous Charge Compression Ignition (HCCI) combustion to hydrogen with the aim of achieving low oxides of nitrogen (NOx) emissions and high fuel economy with the assistance of the di-methyl-ether (DME) fuel supplement. As a result, HCCI combustion of hydrogen mixed with 25 vol% DME achieved approximately a 30% improvement in fuel economy compared with HCCI of pure DME and spark-ignited lean-burn combustion of pure hydrogen under almost zero NOx emissions and low hydrocarbon (HC) emissions. This is attributed to control of the combustion process to attain the optimum onset of combustion and to a reduction of cooling losses.