The derived cetane numbers (DCNs) of the n-dodecane/benzene and n-dodecane/toluene blends were measured using a constant volume combustion chamber facility. The autoignition behaviors of the two sets of fuel blends, including ignition delay (ID) and combustion delay (CD) times, pressure traces, as well as the heat release rates at the DCN determination conditions, that is, 883 K ambient temperature and 20 bar ambient pressure, were also characterized. The results revealed that the n-dodecane/benzene blends have lower DCNs than those of the n-dodecane/toluene blends given the aromatic blending fractions. The two sets of fuel blends exhibit almost the same ID timescales with low aromatic blending fractions, but the ID of the dodecane/toluene blend becomes longer when the aromatic blending fraction rises to 60%. The CDs of the n-dodecane/toluene blends are slightly shorter at low aromatic blending fractions, and this difference becomes more apparent at a higher aromatic blending fraction. The n-dodecane/benzene blends exhibit later heat release starts than the ndodecane/toluene blends given the aromatic blending fractions. With an increased aromatic blending fraction, the heat release processes of the two sets of fuel blends change from a single stage to two stages, and the differences in the heat release behaviors between the two sets of fuel blends increase.