The influence of an Ag/Al2O3 HC-SCR catalyst on the morphological and nanostructural aspects of the exhaust particulate matter (PM) generated during the combustion of diesel fuel and a glycol ether-diesel fuel blend was addressed in this research work. In addition, the impact of in-cylinder fuel post injections (FPI) on the particulate formation pathway and on the catalytic de-NOx efficiency was also studied. The tests were carried at low exhaust temperatures in the absence and presence of small amounts of hydrogen (H-2). It is concluded that in the absence of H-2, the catalyst does not modify the primary particle size (dp(0)) of the soot aggregates, while the aggregation of the soot particles throughout the catalyst channels is the main governing mechanism. The catalyst influence on the particulate structure was evident when H-2 was introduced, with smaller dp(0) seen downstream of the catalyst, indicating that despite the short residence time of the PM within the catalyst bed, the soot particles were partially oxidised. The use of late FPI reduces the exhaust PM level and delivers sufficient HC:NOx ratios that improves the catalyst activity up to a maximum of 80% NOx conversion, with no sign of catalyst deactivation when H-2 (500 ppm) was injected. Furthermore, it is suggested that along with oxidising part of the particles produced during the main fuel injection phase, late FPI can also produce, to a lesser extent, some additional soot with a less matured structure, resulting on average in less ordered particles being emitted into the exhaust stream. This work shows that in modern diesel engines, a silver catalyst can alter the soot structure in the exhaust in a way that can ease the diesel particulate filter (DPF) regeneration cycles, improve its filtration efficiency and help in effectively reducing the tailpipe NOx emissions. For the catalyst to perform these functions, multiple incylinder fuel injection strategies (late FPI) combined with small amounts of hydrogen addition to the exhaust are required.