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The characteristics of exhausted smoke of a methanol DI diesel engine which is ignited by diesel fuel are investigated to clarify the soot formation process. At this engine, very little smoke is exhausted when diesel fuel is kept below a certain amount, so soot and smoke emitting characteristics are studied under the various diesel fuel amounts. By analyzing microstructure of soot, it is found that the soot emitted from the methanol diesel engine is composed of inner core and outer shell, similar to that of the conventional diesel engines. From more detailed qualitative analysis, the calcium percentage from the lubricating oil in outer shell is much higher than that of the conventional diesel engines. In consideration of soot characteristics, spray structure and combustion characteristics, the soot formation process of the methanol diesel engine was clarified.