This study investigated the ozone formation mechanism and air mass trajectory via simultaneous air quality sampling around the coastal region of urban Kaohsiung. Vertical concentration profiles of O3 and its precursors (NOx and VOCs) were sampled and measured at inland and offshore sites during eight intensive sampling periods. The intensive sampling periods were divided into three categories based on meteorological condition: the sea-land breeze period, the northeastern monsoon period, and the mixed period. Vertical profile results showed that the stratification of O3 was commonly observed at 40 out of 64 sampling sites accounting for 62.5% of the total O3 measurement. The results obtained from VOCs measurement indicated that the major species of VOCs was acetone, which accounted for 16.25–64.05% of total TVOCs-C2 in the offshore region, while the major species of VOCs in the inland region was toluene, which accounted for 6.41–43.77 % of total TVOCs-C2. Backward trajectories showed that air pollutants emitted from land sources could transport to the offshore region, resulting in a high concentration of oversea NOx and VOCs. Major species of VOCs with high O3 formation potential were found to be aromatics in the low atmosphere around the coastal region of metro Kaohsiung.