A comprehensive, semi-detailed kinetic scheme was used to simulate the chemical structures of counterflow diffusion and fuel-rich premixed 1,3-butadiene flames, to better understand the formation of polycyclic aromatic hydrocarbons (PAH). The results showed that model predictions were in good agreement with the experiments for most of the species in both the flames. In the counterflow flames higher-molecular weight products are slightly over predicted. The pathways characterizing the pollutant formation are very different in the premixed and in the counterflow flames confirming or suggesting the need to verify and refine the detailed mechanisms tuned for premixed conditions when they are extrapolated and used in diffusion flames. Reaction paths analysis for PAH formation in the counterflow flame shows that both the HACA mechanism and the resonantly stabilized radicals are important for the growth of PAH. The kinetic model was unsuccessful in predicting the increased reactivity in O-2-doped diffusion flames, indicating the need for improved models and also the opportunity of new experiments of butadiene oxidation in the intermediate temperature region.