The municipal solid waste incinerator (MSWI-JW) situated in a highly industrialized area in the Renwu Township, Kaohsiung County of southern Taiwan was chosen to assess the impact of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) emission on ambient air and vegetation. A total of seven ambient air and banyan leaf sites located in the vicinity of the MSWI-JW were sampled and analyzed for PCDD/Fs. The congener profiles of 2,3,7,8 chlorine-substituted PCDD/Fs were selected as the fingerprint, and the PCDD/F congener profile in the stack flue gas of MSWI, and those of the ambient air and the banyan leaf were analyzed by principle component analysis to clarify the pollution sources of the affected receptors. The mean PCDD/F concentration in the stack flue gas was 0.0593 ng I-TEQ/Nm3 (n = 2). The PCDD/F concentration in ambient air ranged between 0.037 and 0.111 and averaged 0.080 pg I-TEQ/Nm3 (RSD: 26.9%; n=14). The PCDD/F composition in banyan leaves ranged between 0.804 and 7.48 and averaged 2.83 ng I-TEQ per kilogram of dry leaves (RSD: 61.9%; n = 14). Whether ambient air or banyan leaf, the relationship between PCDD/F concentration isopleths does not match the geographic position of MSWI-JW and wind rose. The results of PCA analysis coincided with the relationship between PCDD/F concentration isopleths and the geographic position of MSWI-JW and wind rose. These all reveal that the PCDD/F emissions from MSWI-JW have no significant influence on the ambient air and banyan leaf receptors; that is, the MSWI-JW is not responsible for the main contribution of PCDD/Fs in the ambient air and banyan leaf. Other potential emission sources of PCDD/Fs could be of greater importance.