In this study, we produced a class of diffusion flame soot particles with varying chemical and physical properties by using the mini-Combustion Aerosol STandard (CAST) and applying varying oxidant gas flow rates under constant propane, quenching, and dilution gas supply. We varied the soot properties by using the following fuel-to-air equivalence ratios (Φ): 1.13, 1.09, 1.04, 1.00, 0.96, and 0.89. Within this Φ range, we observed drastic changes in the physical and chemical properties of the soot. Oxidant-rich flames (Φ < 1) were characterized by larger particle size, lower particle number concentration, higher black carbon (BC) concentration, lower brown carbon BrC.[BC](-1) than fuel-rich flames (Φ > 1). To investigate the polycyclic aromatic hydrocarbons (PAH) formation online, we developed a new method for quantification by using the one (13)C-containing doubly charged PAH ion in a high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS). The time-resolved concentration showed that the larger PAHs prevailed in the fuel-rich flames and diminished in the oxidant-rich flames. By comparison with the offline in situ derivatization-thermal-desorption gas-chromatography time-of-flight mass spectrometry (IDTD-GC-ToF-MS), we found that the concentration by using the HR-ToF-AMS was underestimated, especially for lower mass PAHs (C14-C18) in the fuel-rich flames possibly due to size limitation and degradation of semi-volatile species under high vacuum and desorption temperature in the latter. For oxidant-rich flames, the large PAHs (C20 and C22) were detected in the HR-ToF-AMS while it was not possible in IDTD-GC-ToF-MS due to matrix effect. The PAH formation was discussed based on the combination of our results and with respect to Φ settings.