It was demonstrated that a series of fluoroalkylated end-capped oligomers containing various functional segments such as carboxy, amide, betaine, and hydroxy groups can be prepared by the use of fluoroalkanoyl peroxides as key intermediates. These thus-obtained fluoroalkylated end-capped oligomers were soluble in water and organic solvents, and were capable of reducing the surface tension of water effectively with a clear break point resembling a CMC, which is almost the same level as that achieved by the usual low molecular weight fluorinated surfactants. This is a unique and interesting feature of our fluoroalkylated end-capped oligo-surfactants. Furthermore, fluoroalkylated end-capped oligomers were suggested to form the molecular assemblies imparted by strong aggregation of the fluoroalkylated end-groups in aqueous solutions, and fluoroalkylated end-capped acrylic acid and sulfonic acid oligomers were also shown to be potent and selective inhibitors of human immunodeficiency virus type 1 (HIV-1) in vitro. More interestingly, fluoroalkylated end-capped oligomers containing betaine or hydroxy segments could cause gelation, where the synergistic interactions of both the strong aggregation of the end-capped fluoroalkyl segments and the ionic or hydrogen-bonding interaction are involved in establishing a gel network in water and polar organic solvents.