The present experimental study aims to examine the impacts of various fueling modes of operation on the particle-phase polycyclic aromatic hydrocarbons (PAHs) and n-alkanes (C16–C30), and volatility and oxidation reactivity of particulate matter (PM) emitted from a diesel engine fueled with a ternary fuel (80% diesel, 5% biodiesel and 15% ethanol (D80B5E15, volume %)) under four engine operating conditions. Four fueling modes, including diesel, blended, fumigation and combined fumigation + blended (F + B) modes were tested using pure diesel fuel for diesel mode and a constant fuel content of D80B5E15 for the blended, fumigation and F + B modes to create the same condition for comparing their impacts on the parameters investigated. The average results illustrate that both blended and fumigation modes can reduce the PAHs (−78.4% and −31.3%), benzo[a]pyrene equivalent (−81.7% and −38.9%), n-alkanes (−46.5% and −21.5%) and non-volatile substance fraction (−25.1% and −11.1%), but increase the high-volatile substance fraction (12.8% and 6.9%) and oxidation reactivity rate (34.0% and 4.9%), respectively compared to those of the diesel mode. While the effect of the blended mode on the parameters investigated is stronger than the fumigation mode. And the F + B mode has the effects in between the results of the blended and fumigation modes.