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Polypyrrole nanofibers are synthesized through a template-free chemical route and used as the active component for hydrogen gas sensing at room temperature. The synthesis of polypyrrole nanofibers was achieved by using bipyrrole as an initiator to speed up the polymerization of pyrrole with FeCl as the oxidizing agent. Scanning and transmission electron microscopy studies indicate that the resulting polypyrrole forms a nanofibrous mat with average nanofiber diameter of 18 nm. Fourier transform infrared spectroscopy and elemental analysis confirms that the structure of the nanofibers is comparable to bulk polypyrrole. Gas sensing properties of polypyrrole nanofibers were investigated by depositing nanofiber dispersions on an interdigited conductometric transducer. The sensor performance was tested through programmable exposure towards different concentrations of hydrogen gas diluted in synthetic air in an environmental cell at different temperatures. A short response time of 43 s was observed upon exposure to a concentration of 1% hydrogen with a decrease in film resistance of 312 at room temperature. The sensor sensitivity was analyzed with gradual elevation of the operating temperature.