Low-temperature compression ignition combustion can result in nearly smokeless combustion, as indicated by a smoke meter or other forms of soot measurement that rely on absorbance due to elemental carbon content. Highly premixed low-temperature combustion modes do not form particulate matter in the traditional pathways seen with conventional diesel combustion. Previous research into reactivity controlled compression ignition particulate matter has shown, despite a near zero smoke number, significant mass can be collected on filter media used for particulate matter certification measurement. In addition, particulate matter size distributions reveal that a fraction of the particles survive heated double-dilution conditions. This study summarizes research completed at Oak Ridge National Laboratory to date on characterizing the nature, chemistry and aftertreatment considerations of reactivity controlled compression ignition particulate matter and presents new research highlighting the importance of injection strategy and fuel composition on reactivity controlled compression ignition particulate matter formation. Particle size measurements and the transmission electron microscopy results do show the presence of soot particles; however, the elemental carbon fraction was, in many cases, within the uncertainty of the thermal–optical measurement. Particulate matter emitted during reactivity controlled compression ignition operation was also collected with a novel sampling technique and analyzed by thermal desorption or pyrolysis gas chromatography mass spectroscopy. Particulate matter speciation results indicated that the high boiling range of diesel hydrocarbons was likely responsible for the particulate matter mass captured on the filter media. To investigate potential fuel chemistry effects, either ethanol or biodiesel were incorporated to assess whether oxygenated fuels may enhance particle emission reduction.