Measurements of speciated non-methane hydrocarbons (NMHCs) were conducted in an ozone non-attainment metropolis with pronounced industrial emissions in addition to traffic ones. Highly variable and complex natures of industrial sources make their composition profiles difficult to determine. In the circumstances of no reliable source profiles, two simple complementary approaches were attempted to characterize sources of NMHCs. First, a robust vehicular indicator, 3-methylpentane (3MC5A), which is an intrinsic component of gasoline, was used to estimate contributions of traffic versus non-traffic sources for major NMHCs with high ozone-forming potentials (OFPs), such as ethene, toluene, xylene, isoprene, etc. Second, the method of principal component analysis (PCA) was employed to further discern non-traffic emissions into various source groups. A total of 454 ambient samples were sampled in the urban-industrial complex metropolis (Kaohsiung, Taiwan) to build up a large dataset to be tested by the two complementary approaches. It was found that four types of emissions, i.e., traffic, household fuel leakage, industrial, and biogenic, were responsible for the observed ambient NMHCs. The industrial contribution was significant for ethene and toluene (with 48-67% and 33-62%, respectively), whereas xylene was found to be mainly vehicular. In addition, isoprene revealed its biogenic nature. OFPs arising from vehicular, industrial and biogenic contributions could be further assessed for the purpose of emission control of NMHCs in the ozone non-attainment area.