The origin of trifluoroacetic acid (TFA) occurring in hydrosphere has long been a controversial issue. Hydrochlorofluorocarbons and hydrofluorocarbons (HCFCs/HFCs) as replacements of chlorofluorocarbons (CFCs) are precursors of TFA in the atmosphere, their contribution to rainwater TFA is a concern as their ambient mixing ratios are continually growing. Here we present rainwater TFA monitored from April 2007 to March 2008 in urban Guangzhou, a central city in south China's highly industrialized and densely populated Pearl River Delta region. Rainwater TFA levels ranged 45.8-974ngL(-1) with a median of 166ngL(-1). TFA levels negatively correlated with rainfall amount, the yearly rainfall-weighted average for TFA was 152ngL(-1). The annual TFA wet deposition flux was estimated to be 229gkm(-2)yr(-1), and the total wet deposition of TFA reached ~1.7tyr(-1) in Guangzhou. The Two-Box model was applied to estimate attributions of HCFCs/HFCs and fluoropolymers to rainwater TFA assuming TFA generated was proportional to gross domestic product (GDP), gross industrial product (GIP) or number of private cars. The results revealed that the degradation of HCFCs/HFCs and fluoropolymers could explain 131.5-152.4ngL(-1) rainwater TFA, quite near the observed rainfall-weighted annual mean of 152ngL(-1), suggesting rainwater TFA in Guangzhou was predominantly originated from these anthropogenic precursors. HCFCs/HFCs accounted for 83.3-96.5% of rainwater TFA observed, while fluoropolymers' contributions were minor (~5%). HFC-134a alone could explain 55.9-90.0% of rainwater TFA, and its contribution would be greatly enhanced with its wide use in mobile air conditioning systems and rapid increase in ambient mixing ratios.