This article aimed at introducing the main physical properties and commercial/industrial uses of common liquid perfluoro-n-alkanes (including perfluoropentane, perfluorohexane, perfluoroheptane, perfluorooctane, and perfluorononane) and the environment and health hazards posed by their toxic decomposition products (especially in hydrogen fluoride and perfluoroisobutylene) because these perfluorocompounds are potent greenhouse gases, which have been blanketed into the Kyoto Protocol, but was rarely described in the National Inventory Reports by Annex I Parties. The environmental properties (including octanol–water partition coefficient, water solubility and Henry’s law constant) of liquid perfluoro-n-alkanes were evaluated, and further discussed were its atmospheric implications according to the predicted properties and possible proposal for the formation of trifluoroacetic acid (CF₃COOH) in the atmosphere by the ionized photolysis. These predicted values revealed that liquid perfluoro-n-alkanes tend to be hydrophobic and partitioned into organic matter, and they have exceptionally low solubility in water and extremely high vaporization from the water bodies, suggesting that it will sink into the atmosphere if it is released into the environment.