The influence of cold fronts on the formation of ozone (O3) pollution, particularly the contributions of physical and chemical processes to O3 abundance during the passage of cold fronts in winter over the Pearl River Estuary (PRE) region was still unclear. This study provided an in-depth analysis on the occurrence of high O3 pollution based on data from field measurements and simulation of a chemical transport model (i.e., WRF-Chem) over the PRE region during winter 2021 when cold fronts were frequently observed. Totally 7 high O3 episode days were observed during pre- and post-frontal stages at DWS (i.e., Da Wan Shan island), a downwind island site of the inland Pearl River Delta (PRD) region, which were accompanied with the prevailing northerly wind patterns with insignificant variations of wind speeds in a stable boundary layer over the whole PRE region. The quantitative analysis based on simulation results indicated that horizontal transport and chemical processes accounted for the buildup of O3 abundance at DWS, with the highest mean rates of 7.3 and 5.6 ppbv/h at pre- and post-frontal stages, respectively. The high contributions from horizontal transport to O3 levels at DWS were associated with the persistent northerly winds with small variations, while the contributions of chemical processes were varied with the abundance of precursors and meteorological conditions. However, vertical transport made negative contributions to O3 abundance, with the most significant mean diffusion rate of −2.6 ppbv/h at the frontal stage because of the control of high-pressure system, while the less influence of vertical transport at pre- and post-frontal stages was associated with the weak pressure gradient forces and wind patterns. The sensitivity analysis further demonstrated that the emissions of precursors from the inland PRD region contributed 50–76% to O3 abundance over PRE at different stages. Overall, the above results quantitatively confirmed the dominant role of transport from inland PRD to the O3 pollution over the downwind PRE region and were helpful for better understanding of O3 pollution in winter over PRE.