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Detailed properties of particulate matter (PM) emissions from a gasoline direct injection (GDI) engine were analyzed in terms of size, morphology, and nanostructures, as gasoline and its ethanol blend E20 were used as a fuel. PM emissions were sampled from a 0.55L single-cylinder GDI engine by means of a scanning mobility particle sizer (SMPS) for size measurements and a self-designed thermophoretic sampling device for the subsequent analyses of size, morphology and nanostructures using a transmission electron microscope (TEM). The particle sizes were evaluated with variations of air-fuel equivalence ratio and fuel injection timing. The most important result from the SMPS measurements was that the number of nucleation-mode nanoparticles (particularly those smaller than 10 - 15 nm) increased significantly as the fuel injection timing was advanced to the end-of-injection angle of 310° bTDC.