Perfluorinated alkyl acids (PFAs) belong to a family of chemicals that are highly persistent and potentially ecotoxic. They are under scrutiny by government agencies who must determine their risk to humans and the environment. Numerous studies have measured perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) in selected areas of the world, but there has been no systematic cross-Canada study of these compounds in surface waters. This report describes the concentrations of PFAs in 38 rivers across Canada (42 to 60°N and 62 to 136°W). Samples were collected upstream and downstream of populated areas. PFOS and PFOA were the predominant PFAs detected. Values of PFOS ranged from <0.020 to 34.6 ng/L and PFOA ranged from 0.044 to 9.9 ng/L. Highest concentrations occurred in areas of high population densities, generally at downstream sites. The shorter chain perfluorocarboxylates (PFCAs) (C6)to C9) were present in most samples but the longer chain PFCAs (C10 to C14) were not often detected. Perfluorohexane sulfonate was the next most frequently detected perfluoroalkylsulfonate while perfluoro-1-octanesulfonamide (PFOSA) was detected infrequently.