Thermoplastic polyurethane (TPU) functionalized with azido groups is useful because not only it allows the convenient introduction of various desired functional groups via the azide-alkyne click reaction, but also it is elastic, flexible, and easily proccessable. However, after undergoing click reaction with useful functional groups on polymer chain directly, the polymer becomes hard and non-soluble in organic solvents, losing its useful properties. Therefore, a surface click reaction is performed on the azido TPU electrospun fiber to introduce specific functional groups (here amine and guanidine for catalytic reaction). The amine- and guanidine-treated TPU fibers effectively convert diisopropyl fluorophosphatesthe simulant of toxic nerve gasesand 2,2-dichlorovinyl dimethyl phosphateone of the insecticides to a non-toxic product via decontamination by hydrolysis, with the amine and guanidine functional groups acting as nucleophilic catalysts. (c) 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46519.