The effects of adding acetylene to the fuel stream on soot formation and flame properties were investigated numerically in a laminar axisymmetric coflow ethylene/air diffusion flame using the open-source flame code Co-Flame in conjunction with an elementary gas-phase chemistry scheme and detailed transport and thermodynamic database. Radiation heat transfer of the radiating gases (H2O, C2H2, CO, and CO2) and soot was calculated using a statistical narrow-band correlated-k-based wide band model coupled with the discrete-ordinates method. The soot formation was described by the consecutive steps of soot nucleation, surface growth of soot particles via polycyclic aromatic hydrocarbons (PAHs)-soot condensation or the hydrogen abstraction acetylene addition (HACA) mechanism, and soot oxidation. The added acetylene affected the flame structure and soot concentration through not only chemical reactions among different species but also radiation effects. The chemical effect due to the added acetylene had a significant impact on soot formation. Specifically, it was confirmed that the addition of 10% acetylene caused an increase in the peak soot volumetric fraction (SVF) by 14.9% and the peak particle number density by about 21.1% (z = 1.5 cm). Furthermore, increasing acetylene concentration led to higher concentrations of propargyl, benzene, and PAHs and consequently directly enhanced soot nucleation rates. In addition, the increased H mole fractions also accentuated the soot surface growth. In contrast, the radiation effect of the addition of 10% acetylene was much weaker, resulting in slightly lower flame temperature and SVF, which in turn reduced the radiant heat loss.