A field sampling campaign of volatile organic compounds (VOCs) was conducted during ozone polluted days at three sites of botanic gardens (HP), industrial areas (XS), and traffic residential mixed areas (ZH) in Hangzhou. The sampling was performed using stainless steel canisters from 6:00 to 20:00 synchronously with a time interval of 2 h on 17 May, 26 June, 20 July, 24 August, and 26 September 2018. A total of 107 species of VOCs for each sample were quantified using two standard gases with a pre-concentrator coupled by GC/MS. The Positive Matrix Factorization (PMF) model was used to identify the major VOC sources and assess their contribution to VOC concentrations. The effects of VOCs on O3 formation were investigated, based on propylene-equivalent concentrations (Prop-E), ozone formation potential (OFP), and Smog Production Model (SPM). It was found that the concentration of ozone during the sampling days tended to be highest in the downwind area while the concentrations of VOCs and NO2 in HP were rather low. The most reactive species were isoprene, ethylene, m-xylene, toluene, and propylene. The average total VOC volume mixing ratios in HP, XS, and ZH were 32.00, 36.63, and 50.34 ppbv, respectively. Bimodal profiles of propane and n-butane were exhibited in ZH while unimodal diurnal variation of isoprene was performed in HP. Liquefied petroleum gas/natural gas (LPG/NG) usage, aged background, and secondary source were identified as the major contributors to total VOCs in Hangzhou, accounting for 19.65%, 15.53%, and 18.93%, respectively.