Fluoropolymer manufacturing is a major historical source of perfluorooctanoic acid (PFOA) on a global scale, but little is known about the emissions, transport, and fate of emerging per- and polyfluoroalkyl substances (PFASs). Here, we performed a comprehensive spatial trend and interyear comparison of surface water and sediment samples from the Xiaoqing River, which receives water discharge from one of the major fluoropolymer manufacturing facilities in China. A suspect screening identified 42 chemical formulas, including the tetramer acid of hexafluoropropylene oxide (HFPO-TeA) and numerous tentatively detected isomers of C9-C14 per- or polyfluoroalkyl ether carboxylic acids (PFECAs). As revealed by the spatial trends and peak area-based sediment-water distribution coefficients, emerging PFASs with 3-9 perfluorinated carbons were transported unimpededly with the bulk water flow having no measurable degradation. Emerging PFASs with >9 perfluorinated carbons displayed more rapidly decreasing spatial trends than shorter-chain homologues in surface water due to increasing sedimentation rates. The presence of HFPO oligomers, monoether PFECAs, monohydrogen-substituted perfluoroalkyl carboxylic acids (PFCAs) and monochlorine-substituted PFCAs could partly be explained by the active use of polymerization aids or the impurities therein. However, further research is encouraged to better characterize the emissions of low-molecular-weight PFASs from fluoropolymers throughout their life-cycle.