The effect of rail pressure and biodiesel fueling on the morphology of exhaust particulate agglomerates and the nanostructure of primary particles (soot) was investigated with a common-rail turbocharged direct injection diesel engine. The engine was operated at steady state on a dynamometer running at moderate speed with both low (30%) and medium?high (60%) fixed loads, and exhaust particulate was sampled for analysis. Ultra-low sulfur diesel and its 20% v/v blends with soybean methyl ester biodiesel were used. Fuel injection occurred in a single event around top dead center at three different injection pressures. Exhaust particulate samples were characterized with TEM imaging, scanning mobility particle sizing, thermogravimetric analysis, Raman spectroscopy, and XRD analysis. Particulate morphology and oxidative reactivity were found to vary significantly with rail pressure and with biodiesel blend level. Higher biodiesel content led to increases in the primary particle size and oxidative reactivity but did not affect nanoscale disorder in the as-received samples. For particulates generated with higher injection pressures, the initial oxidative reactivity increased, but there was no detectable correlation with primary particle size or nanoscale disorder.