The characteristics and sources of major hydrocarbons and halocarbons in the wintertime ambient air of urban center of Shanghai, a mega city of China, were investigated. Propane, toluene, ethyl acetate, and benzene were the most abundant hydrocarbons. The majority of species showed significant variability in mixing ratios with occasional episodic increases. The more common use of liquefied petroleum gas fuel for taxis and light motorcycles was believed to lead to high levels of ambient propane over the urban center of Shanghai. Correlating with toluene, dichloromethane, and 1,2-dichloroethane (1,2-DCE), abundant chloromethane (up to a daily mean of 1.61 ± 0.99 ppbv and a maximum of 5.34 ppbv) was mainly associated with industrial emissions, although biomass burnings exist widely in east China. The Chinese New Year (CNY) holiday period with no industrial activity over China provides a platform for the study of industrial emissions over the urban atmosphere of Shanghai. The normal weekly cycles were characterized by higher and more variable mixing ratios during weekdays which dropped during weekends. Enhanced mixing ratios were observed in the fortnight before the CNY holidays due to increased industrial emissions as a result of overtime production to make up for the holiday losses. During the CNY holidays, lower level and less variable mixing ratios were observed. A benzene/toluene (B/T) ratio of 0.6 ± 0.4 (mean ± std.) for the morning rush hour samples was identified to be the characteristic ratio of vehicular emissions. However, a B/T ratio of 0.4 ± 0.2 from vehicles and other sources was derived for the ambient air.