The emission inventory, emission factor, and spatial concentration distribution of volatile organic compounds (VOCs) from a petrochemical industry (aromatics plant) were intensively evaluated in this study to elucidate the potential sources of BTX emission and their contribution to ambient concentrations. Five emission groups were quantified through direct measurement and emission models. These data were then used as input for the AERMOD dispersion model for the source apportionment analysis. The source to ambient contribution analysis revealed that a wastewater treatment facility and organic liquid storage tank were major contributors accounting for about 20.6–88.4% and 10.3–75.4% to BTX environmental concentrations, respectively. The highest annual ambient concentrations of benzene (B), toluene (T), and xylenes (X) were predicted as 9.0, 2.8, and 57.9 µg/m3 at the fence line of the plant boundary, respectively. These findings assist policymakers in prioritizing the appropriate control measures to the right source by considering not just the amount released but also their contribution to ambient concentrations. This study suggested that the wastewater treatment unit should be changed to the closed system which will benefit reduction in its emission (45.05%) as well as effectively minimizing ambient VOC concentration by 49.96% compared to its normal operation.