A wide range of volatile organic solvents, including aliphatic and aromatic hydrocarbons, alcohols, and ketones, are used in the production of paints, and they comprise more than 30% of the ingredients of paints. The present study was designed to evaluate the occupational exposure to 15 volatile organic compounds (VOCs, including benzene, toluene, ethylbenzene, xylene, styrene, n-hexane, n-heptane, n-nonane, trichloroethylene, tetrachloroethylene, n-butyl acetate, n-octane, n-decane, dichlorofluoromethane, and acetone) in Iranian paint production factories and subsequently, the associated health risks. The samples were collected from the respiratory zone of workers using the NIOSH 1501 method, and their qualitative and quantitative characterization was performed using gas chromatography-mass spectrometry and gas chromatography-flame ionization detector, respectively. The individual concentrations of VOCs ranged from 23.76 ± 0.57 µg m−3 (acetone) to 92489.91 ± 0.65 µg m−3 (m,p-xylene). The predominant compounds were m,p-xylene (up to 92489.91 ± 0.65 µg m−3), ethylbenzene (up to 91188.95 ± 0.34 µg m−3), and toluene (up to 46088.84 ± 0.14 µg m−3). The non-cancer risks of benzene, n-nonane, trichloroethylene, tetrachloroethylene, xylene, and ethylbenzene surpassed the reference value in most of the sectors. In addition, total lifetime risks of cancer were in the range of 1.8 × 10−5–3.85 × 10−3, suggesting that there was a risk of carcinogenesis in all studied sections, mainly due to ethylbenzene and benzene. Considering their high exposure concentrations and their associated non-carcinogenic and carcinogenic risks, biological monitoring of workers and the use of technical and modern engineering control measures are recommended.