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Improving the technical performance of related industrial products is an efficient strategy to reducing the application quantities and environmental burden for toxic chemicals. A novel polyfluoroalkyl surfactant potassium 1,1,2,2,3,3,4,4-octafluoro-4-(perfluorobutoxy)butane-1-sulfonate(F404) was synthesized by a commercializable route. It had a surface tension(γ) of 18.2 mN/m at the critical micelle concentration(CMC, 1.04 g/L), significantly lower than that of perfluorooctane sulfonate(PFOS, ca. 33.0 mN/m, 0.72 g/L), and exhibited remarkable suppression of chromium-fog at a dose half that of PFOS. The half maximal inhibitory concentration(IC 50 ) values in HepG2 cells and the lethal concentration of 50%(LC50) in zebrafish embryos after 72 hpf indicated a lower toxicity for F404 in comparison to PFOS. In a UV/sulphite system, 89.3% of F404 were decomposed after 3 h, representing a defluorination efficiency of 43%. The cleavage of the ether C—O bond during the decomposition would be expected to form a short chain·C 4 F 9 as the position of the ether C—O in the F404 fluorocarbon chains is C4—O5. The ether unit is introduced in the perfluoroalkyl chain to improve water solubility, biocompatibility and degradation, thereby minimizing the environmental burden. Electronic Supplementary Material Supplementary material is available in the online version of this article at 10.1007/s40242-023-3030-4.