Continuous on-site measurements of 50 speciated volatile organic compounds (VOCs) were conducted in downtown Guangzhou to characterize the sources and concentration profiles of ambient VOCs. The synchronicity in diurnal variation between the VOCs and NO suggests that traffic emissions were responsible for the observed VOCs in downtown Guangzhou. It was found that the three major constituent species of liquefied petroleum gas (LPG), i.e., propane, iso-butane, and n-butane, together termed LPG alkanes, contributed, on average, 24% of the total VOCs (TVOCs). Their high correlation and synchronized diurnal variations between NO and the LPG alkanes suggest that their origin lies in LPG fueled car exhaust in Guangzhou. LPG buses and taxis were likely to be responsible for the bulk of ambient LPG species. Using propane and 3-methyl pentane (3MC5A) as the indicators for the LPG and gasoline emissions, respectively, the emissions of the LPG fleet were found to increase more than those of the gasoline fleet during the morning and evening rush hours, as well the noontime break in downtown Guangzhou. Although LPG alkanes account for 24% of the TVOC, their contribution to the total ozone forming potential (OFP) is only about 7%. Ethylene and propylene contribute about 26% to the total OFP despite their lower contribution of 16% to the TVOC.