Manufacturing industries are one of the important emission sectors of anthropogenic volatile organic compounds (VOCs). In this study, VOC emission factors, relative ozone formation potential (ROFP) and relative carcinogenic risk (RCR) were estimated for some important manufacturing industries (n = 13) located in central Taiwan. Emission samples were collected in stainless steel canisters and were analyzed with a system of gas chromatography-mass spectroscopy. Higher emission factors of total VOCs (∑VOCs) were observed for stencil printing (423 mg-VOC kg-1) compared to other emission industries. Alkanes constituted the most prominent group of VOCs for steel foundry (41.6%), aluminum foundry (25.1%) and synthetic resin industries (25.0%). Oxygenated VOCs were obtained as the most abundant group in the organic solvent (80.3%), polyester resin (80.0%) and PU leather (75.0%) industries. Moreover, emissions from acrylic resin manufacturing had higher contributions from aromatic compounds (> 95%). Toluene was the topmost compound in terms of its contribution to ∑VOCs in plastic tape manufacturing (44.4%), aluminum foundry (39.6%), steel foundry (11.6%), plastic coating (64.3%) and stencil printing (35.3%). Analysis of ozone formation potentials showed that the metal product and machinery acrylic resin manufacturing and stencil printing had a higher normalized ROFP index and belonged to Level-I emission sources. However, in terms of the RCR, integrated iron and steel manufacturing had the highest normalized RCR index belonged to level-I emission sources. Level-I represents the most important VOC emission sources. This study provides a reactivity- and carcinogenicity-based approach to identify high-priority VOC emission sources. The results of this study would help formulate emission reduction policies and strategies for manufacturing industries.