Abstract Perfluorooctanoate (PFOA) and other perfluorocarboxylates (PFCAs) are widely dispersed in the environment. Current and/or historical production of PFOA and fluorochemical precursors was conducted by telomerization and electrochemical fluorination (ECF). Telomer products typically contain linear chains of perfluorocarbons, and ECF products are a mixture of linear and branched isomers. The objective of the present study was to examine the role of toxicokinetics on PFCA isomer profiles in fish since monitoring studies have revealed a predominance of n-isomers of PFCAs in biota. Using dietary exposure, rainbow trout were administered technical ECF PFOA isomers (6.9 μg/kg/d), linear perfluorononanoate (1.4 μg/kg/d n-PFNA), and isopropyl PFNA (1.1 μg/kg/d iso-PFNA) for 36 d and then switched to a 40-d clean diet. Throughout exposure and depuration phases, blood and tissue sampling ensued. The accumulation ratio (AR) revealed similar accumulation propensity of n-PFOA and two minor branched PFOA isomers; however, the majority of branched isomers had lower AR values than n-PFOA. Enrichment of n-PFOA and n-PFNA relative to most branched isomers was consistent in all tissues. First-order elimination (kd) and half-life (t1/2) values were calculated. The largest t1/2 corresponded to n-PFNA followed by iso-PFNA. In ECF PFOA isomers, both n-PFOA and one minor branched isomer had the largest t1/2, suggesting that this minor isomer could be diagnostic of ECF exposure using environmental PFOA isomer patterns. Results of lower-dose ECF PFOA exposure showed similar results to the high-dose study; it is possible that both scenarios resulted in saturation of processes involved in PFCA transport. As such, the toxicokinetics of PFCA isomers at environmentally realistic levels may deviate from the results of the present study.