Traditionally the fluorous phase is generated with perfluorinated alkyl groups that are usually perfluorooctyl or longer and are bioaccummulative and biopersistent and therefore, are considered environmentally unfriendly. Here we report a new concept for the construction of the fluorous phase. This concept is based on the amplification of the fluorous effect with the help of dendritic architectures containing very short semifluorinated groups on their periphery. This new concept was demonstrated by the convergent synthesis of the first and second generation AB(3) and AB(2) benzyl ether dendrons functionalized on their periphery via catalytic nucleophilic addition of their phenolates to perfluoropropyl vinyl ether. The resulting dendrons are liquids. Their fluorous phase affinity was analyzed and demonstrated that the dendritic architecture amplifies the fluorous phase at a specific generation by the number of functional groups on the dendron periphery, and at different generations by increasing their generation number. Therefore, this concept is very efficient for the design and synthesis of new fluorous materials. In addition, by contrast with dendrons containing perfluoroalkyl groups on their periphery, the current dendrons mediate the disassembly of their parent building blocks but do not mediate the self-assembly in a supramolecular architecture. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2498-2508, 2010