Volatile organic compounds (VOCs) are key precursors of photochemical smog. Quantitatively evaluating the contributions of VOC sources to ozone (O3) formation could provide valuable information for emissions control and photochemical pollution abatement. This study analyzed continuous measurements of VOCs during the photochemical season in 2014 at a receptor site (Heshan site, HS) in the Pearl River Delta (PRD) region, where photochemical pollution has been a long-standing issue. The averaged mixing ratio of measured VOCs was 34±3 ppbv, with the largest contribution from alkanes (17±2 ppbv, 49 %), followed by aromatics, alkenes and acetylene. The positive matrix factorization (PMF) model was applied to resolve the anthropogenic sources of VOCs, coupled with a photochemical-age-based parameterization that better considers the photochemical processing effects. Four anthropogenic emission sources were identified and quantified, with gasoline vehicular emission as the most significant contributor to the observed VOCs, followed by diesel vehicular emissions, biomass burning and solvent usage. The O3 photochemical formation regime at the HS was identified as VOC-limited by a photochemical box model with the master chemical mechanism (PBM-MCM). The PBM-MCM model results also suggested that vehicular emission was the most important source to the O3 formation, followed by biomass burning and solvent usage. Sensitivity analysis indicated that combined VOC and NOx emission controls would effectively reduce incremental O3 formation when the ratios of VOC-to-NOx emission reductions were > 3.8 for diesel vehicular emission, > 4.6 for solvent usage, > 4.6 for biomass burning and 3.3 for gasoline vehicular emission. Based on the above results, a brief review of the policies regarding the control of vehicular emissions and biomass burning in the PRD region from a regional perspective were also provided in this study. It reveals that different policies have been, and continue to be, implemented and formulated and could help to alleviate the photochemical pollution in the PRD region. Nevertheless, evaluation of the cost-benefit of each policy is still needed to improve air quality.