Toluene is one of the most important precursor contributors to ozone and secondary organic aerosol (SOA), both of which greatly affect the air quality and human health. In this study, the effects of toluene on ozone and SOA formation were investigated in the presence of NOx in the CAPS-ZJU (Complex Air Pollution Study-Zhejiang University) smog chamber. Three comparison groups of experiments were conducted under the gas-phase environments of toluene/NOx, toluene/isoprene/NOx, and toluene/ethylene/NOx. The ozone concentration and physical properties of SOA such as mass concentration, aerosol yield, effective density, extinction and scattering were measured simultaneously. A toluene-dependent mechanism of ozone formation was found at ratios of toluene and NOx between 3.1 and 11.3 with the initial NOx concentration about 30 ppb. With further increase of the toluene concentration, the maximum value of ozone concentration remained almost stabilized. The maximum SOA yields decreased with increase of toluene, while the SOA effective density was concentrated at 1.3–1.4 g cm–3. The presence of isoprene or ethylene can promote the formation of ozone and SOA. The SOA nucleation was delayed under different initial toluene concentrations and the yield was reduced at the same mass concentration. A linear increase of extinction and scattering was observed with the increase of SOA mass concentration in both the toluene/isoprene/NOx and toluene/ethylene/NOx systems. A rapid increase of single scattering albedo reflects the process of SOA nucleation and growth. In addition, organic aerosol oxidation products tend to carboxylic acids in toluene/isoprene/NOx system according to Van Krevelen.