Abstract: The concentrations of 59 VOCs species in the atmosphere of industrial cluster area in Zibo City was detected using VOCs online rapid continuous automatic monitoring system. The results indicated that the average VOCs concentration was (130.74±63.42)×10^-9(volume fraction, the same all the article) during the observation period. The order of volume fraction of each VOCs species was alkanes (41.17%±17.67%),alkenes (34.22%±23.79%),sulphur-containing VOCs (12.20%±20.83%),aromatics (6.70%±10.39%),alkyne (5.75%±6.49%). Alkenes VOCs, especially ethylene, cis-2-butene and propylene, had the highest activity, and had the highest photochemical reactivity. Two typical periods with different VOCs and O₃ concentrations were selected to estimate the frontier orbital energy difference between the detected sulphur-containing VOCs and ·OH by quantum chemical molecular simulation. Sulfur-containing VOCs(methyl mercaptan, methyl sulfide, dimethyl disulfide) were more likely to cause chain reactions with ·OH. The effects of VOCs components on ozone formation were analyzed in the two periods, which showed that when the concentrations of alkenes and aromatics were not high, ozone was still at a high level due to the increase of sulphur-containing VOCs concentration, and sulphur-containing VOCs became the main contributors of ozone in the atmosphere. According to the sensitivity of VOCs/NO_x, it was found that ozone formation in Zibo City was sensitive to VOCs during the observation period, and Zibo City belonged to VOCs control area.